Photocatalytic, fluorescent BiPO4@Graphene oxide based magnetic molecularly imprinted polymer for detection, removal and degradation of ciprofloxacin

Journal Pre-proof Photocatalytic, fluorescent BiPO4@Graphene oxide based using magnetic nanoparticles as adsorbentmagnetic molecularly imprinted polymer for detection, removal and degradation of ciprofloxacin

Sunil Kumar, Paramita Karfa, Kartick Chandra Majhi, Rashmi Madhuri PII:

S0928-4931(19)33938-4

DOI:

https://doi.org/10.1016/j.msec.2020.110777

Reference:

MSC 110777

To appear in:

Materials Science & Engineering C

Received date:

22 October 2019

Revised date:

28 January 2020

Accepted date:

24 February 2020

Please cite this article as: S. Kumar, P. Karfa, K.C. Majhi, et al., Photocatalytic, fluorescent BiPO4@Graphene oxide based using magnetic nanoparticles as adsorbentmagnetic molecularly imprinted polymer for detection, removal and degradation of ciprofloxacin, Materials Science & Engineering C (2020), https://doi.org/10.1016/j.msec.2020.110777

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© 2020 Published by Elsevier.

Journal Pre-proof Photocatalytic, fluorescent BiPO4@Graphene oxide based magnetic molecularly imprinted polymer for detection, removal and degradation of ciprofloxacin Sunil Kumar,* Paramita Karfa, Kartick Chandra Majhi, Rashmi Madhuri Department of Chemistry, Indian Institute of Technology (Indian School of Mines), Dhanbad,

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Jharkhand 826 004, INDIA

Author: (S. Kumar), Tel: +91 7367022144; email: [email protected] Author: (R. Madhuri), Tel: +91 9471191640; email: [email protected]

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Journal Pre-proof Abstract Herein, we have developed a photocatalytic, fluorescent bismuth phosphate@graphene oxide (BiPO4@GO) based magnetic nano-sized-molecularly imprinted polymer (MMIP) for detection, removal, and degradation of ciprofloxacin (CIP) via atom transfer radical polymerization (ATRP) process. CIP is a very popular antibiotic, but their heavy doses in recent time, made them an environmental threat. The imprinted polymer was synthesized using N-vinyl caprolactam, N, N-methylene bis-acrylamide, ZnFe2O4 nanoparticle, and Bi(PO4)@GO as a biocompatible monomer, crosslinker, magnetic moiety, and photocatalyst, respectively. The characterization of the molecularly imprinted polymer was systematically

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evaluated by electrochemical techniques, X-ray diffraction, fluorescence spectroscopy,

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scanning electron microscopy, etc. The prepared BiPO4@GO modified CIP-imprinted magnetic polymer (BiPO4@GO-MMIPs) shows high selectivity towards their template/target

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analyte (i.e., CIP) and used for their visual (via fluorescence study) and trace level detection (via the electrochemical study) in various kind of complex matrix. The dual behaviour i.e.

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electrochemical and optical sensing of CIP was successfully achieved in a good linear range of 39.0 to 740.0 μg L-1 with detection of limit (LOD) of 0.39 μg L-1 for electrochemical study

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and 39.0 to 328.0 μg L-1 and LOD of 0.40 μg L-1 for optical study. The prepared BiPO4@GOMMIPs were successfully used for the detection of CIP from complex matrix like blood

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efficiency.

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serum, whole blood, and milk sample as well as removal and degradation of CIP with good

Keywords: Imprinted polymers; ciprofloxacin; ZnFe2O4 nanoparticle; Bi(PO4)@GO; photocatalyst; real sample analysis.

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Journal Pre-proof 1.

Introduction Water pollution is a severe and lethal problem all over the world from an ancient age.

With an increase in our day by day industrial, agricultural, and domestic activities, this problem is also increasing with the introduction of new kinds of pollutants. In the new category of water pollutants, pharmaceutical products like antibiotics are at the top, owing to the research of new medicines and their high consumption. With the increasing rate of antibiotic use, it is going to be tough to tackle the rising concentration of antibiotic residues in the aquatic system and drinking water supply. Ciprofloxacin (CIP) is a very popularly used antibiotic with very high antibacterial

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activity, belongs to the class of fluorocloroquinol. However, in recent times, CIP can be very frequently detected in drinking water, household polluted water (0.09 to 6.0 μg L-1), cow milk

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(0.1-100 ng mL-1) [1], and wastewater having a concentration range of ng L-1 to μg L-1 [2].

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The frequent contamination of CIP in water makes them an important water pollutant, and therefore it is high time to develop sensitive and selective tools/techniques for trace level

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detection of CIP in food products and supplied water. However, the problem cannot be solved by just detecting the CIP residues; to sort out this problem from their root, we need a

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technique, which will not only identify the CIP but remove or degrade it. Unfortunately, the conventional and earlier reported methods have focused on a single

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aspect of this problem only, and several pieces of literature have been reported for either detection [3] or removal/degradation [4, 5] of CIP from various kinds of food products and

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water supplies. Several methods including immunoassay [6], high-performance liquid chromatography (HPLC) [7], and enzyme-linked immunosorbent assay (ELISA) [8], spectrophotometry [9], mass spectrophotometry [10], fluorescence spectroscopy [11], solidphase extraction [12], capillary electrophoresis [13], and electrochemical techniques [14] were investigated for detection as well as removal of CIP. All these methods have claimed to be accurate and showed a good detection limit but do not possess selectivity towards CIP, which may influence their results and response in the complex matrices. Besides, the majority of such techniques require long analysis time, more cost, complicated and sophisticated instruments, and operated or used by experienced personnel only. To improve the selectivity of these techniques, some of the researchers have reported molecularly imprinted polymers (MIPs) based methods for removal or detection of CIP. MIPs are synthetic materials designed to mimic the antibody-antigen kind of interaction and have attracted the attention of researchers in the last decade [15-22]. MIP based sensor or separation techniques possess several advantages (like low cost, easy to prepare), but above 3

Journal Pre-proof any of their special property, MIPs are made to selectively identify their target molecule, avoiding any kind of complex matrix. However, owing such a good selectivity towards their target molecule, MIPs based sensing or separation technology are very limited in comparison to other popular sensing and separation techniques like electrochemical sensing, chromatographic separation, etc This may be attributed to their poor template extraction and poor distribution of heterogeneous recognition sites [20-24]. To overcome these problems, in recent times, MIPs have been incorporated with nanomaterials, which can improve their binding ability as well as the distribution of recognition sites. For example, Zhu et al. have prepared water-compatible molecularly imprinted polymer in water medium for the

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determination of CIP [25]. Kuhn et al. have investigated the magnetic molecularly imprinted

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polymer by a microemulsion polymerization process for the detection of ciprofloxacin [26]. In different literature, a dual-template imprinting polymer based on dispersive solid-phase

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extraction, coupled with high-performance liquid chromatography, was synthesized by Li at al. for the detection of fluoroquinolones [27]. Okan et al. have reported a molecularly

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imprinted polymer-based micromechanical cantilever sensor system for the selective determination of CIP [28]. While Yuphintharakun et al. have reported an opto-sensor was

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containing carboxylic functionalized multiwall carbon nanotubes and quantum dots incorporated into molecularly imprinted polymer for highly selective and sensitive detection

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of CIP [29]. However, to date, no one has tried for selective detection as well as separation/degradation of CIP from real-samples.

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Taking consideration of all the drawbacks of existing detection/removal techniques reported so far for CIP, we have developed here photocatalytic, fluorescent bismuth phosphate@graphene oxide (BiPO4@GO) based magnetic MIP for detection, removal, and degradation of CIP via atom transfer radical polymerization (ATRP) process. In this work, each component used to prepare the CIP-imprinted polymer has its own advantages. Like, BiPO4@GO nanomaterial possesses photocatalytic, and fluorescent properties, which can be attributed to the presence of BiPO4. In recent time, BiPO4 has gained lots of importance towards photocatalytic degradation of water pollutant using UV-visible light [30] and have a suitable band gap (Eg) of 3.85 eV [31] while GO has provided large specific surface area, high electrical conductivity and good adsorption capacity to the prepared nanocomposite material. The combination of Bi(PO4) with GO gives an improved absorption range and enhanced photocatalytic activity [32]. In order to introduce the magnetic properties in the prepared MIP, ZnFe2O4 nanoparticles (NPs) were used in the core of the polymer matrix. Additionally, the N-vinyl caprolactom is used as one of the monomers, which introduced 4

Journal Pre-proof biocompatibility in the prepared imprinted polymer [33]. Therefore, altogether, the prepared BiPO4@GO modified CIP-imprinted magnetic polymer (BiPO4@GO-MMIPs) shows high selectivity towards their template/target analyte (i.e., CIP). The prepared imprinted polymer was used for visual (via fluorescence study) and trace level detection (via the belectrochemical study) of CIP in various kinds of complex matrices. Additionally, the prepared BiPO4@GO-MMIPs were used for separation/removal of CIP from the complex matrix and used for their complete degradation under UV-visible light. 2.

Experimental section

2.1

Reagents and Instrumentation

triethoxyvinylsilane,

2-bromoisobutyryl

bromide,

toluene,

3-

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ammonia,

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Ciprofloxacin (CIP), Ferric nitrate [Fe(NO3)3.5H2O], Zinc acetate [Zn(OAc)2.2H2O], aminopropyltriethoxysilane (APS), triethylamine (TEA), bismuth nitrate [Bi(NO3)2.5H2O],

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nitric acid, graphite powder, sodium hydroxide (NaOH), methanol, potassium permanganate (KMnO4), (HNO3), sulfuric acid (H2SO4), phosphoric acid (H3PO4), dimethylsulphoxide

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(DMSO), ethanol, sodium dihydrogen phosphate, and disodium hydrogen phosphate were procured from Spectrochem Pvt. Ltd. (Mumbai, India). Hydrogen peroxide (H2O2), HCl,

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vinyl triethoxy silane, cuprous Bromide (CuBr), and 2, 2’-Bipyridyl, N, N’-methylene bisacrylamide were received from Aldrich, Steinheim, Germany. Arginine, adenine, potassium

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ferrocyanide, and N-vinylcaprolactam were purchased from Merck, Mumbai, India. Pencil

(Mumbai, India).

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rods (2B grade, 0.5 mm diameter, 5 cm length) were purchased from Hi Par, Camlin Ltd.

All electrochemical studies including square wave stripping voltammetry (SWSV) and cyclic voltammetry (CV) were performed using three-electrode cell, consist of platinum wire (as counter electrode), Ag/AgCl (3.0 M KCl) (as reference electrode), and BiPO4@GOMMIPs-modified PGE (as working electrode) on the CH instrument (USA, model number 440C) at IIT (ISM) Dhanbad. XRD was obtained using Ultima IV (Rigaku) JMI (Delhi), UVvis spectra were obtained by using SHIMADZU, UV-1800 (Germany), Morphological image of prepared materials was recorded on field emission scanning electron microscope (FESEM), ZEISS MERLIN VP Compact at IIT (ISM) Dhanbad. High-Resolution Transition Electron Microscope (HR-TEM), images were recorded by using Jeol/JEM 2100 model with LaB6 source at Sophisticated Test and Instrumentation Centre, Cochin, India.

Fourier

transform Infrared (FTIR) spectra was performed by using Fourier transform infrared [FT-IR] spectrometer (Perkin Elmer) at IIT (ISM) Dhanbad. HORIBA Fluoromax-4CP (USA) spectrophotometer was used for the analysis of materials under the normal condition. 5

Journal Pre-proof Vibrating Sample Magnetometer (VSM) analysis of samples was performed at IIT-Kanpur (ADE-DMS VSM, model No. -EV7, USA). The calibration equation was calculated using Microsoft excel. 2.2

Synthesis of BiPO4@GO modified CIP-imprinted magnetic polymer The schematic diagram showing the synthesis of BiPO4@GO modified CIP-imprinted

magnetic polymer (BiPO4@GO-MMIPs) is portrayed in Scheme 1, Scheme S1, and Scheme S2. In brief, the synthesis was performed in three steps. In the first step, 2-Bromo-2-methylN-3-(tri-ethoxysilyl) propanamide (BTPAm) modified ZnFe2O4 NPs was synthesized. In the second step, triethoxy vinyl silane-modified BiPO4@GO was synthesized. In the final step,

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all the prepared nanomaterials, monomers, and cross-linker were polymerized together to

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form BiPO4@GO-MMIPs.

2.2.1 Preparation of 2-Bromo-2-methyl-N-3-(tri-ethoxysilyl) propanamide (BTPAm)

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For the synthesis of BTPAm [34], 0.8 mmol of 2-bromoisobutyryl bromide (dissolved in 10 mL toluene) and 0.8 mmol of 3-aminopropyl triethoxysilane (dissolved in 10 mL

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toluene) were mixed together followed by addition of 0.8 mmol trimethylamine in a round bottom flask. The solution was stirred for 2 h at 0 ºC, under a nitrogen atmosphere, and then

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stirred for 24 h at room temperature. The solvent was evaporated by rota vapour, and the resulting product (BTPAm) was separated by ethyl alcohol.

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2.2.2 Synthesis of BTPAm modified ZnFe2O4 NPs ZnFe2O4 NPs were prepared by a convenient one-step solvothermal method [35]. In

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brief, 3.52 g of Fe(NO3)2.5H2O was dissolved in 35 mL of ethanol, followed by the addition of 1.3g Zn(OAc)2.2H2O. The mixture was stirred for 10 minutes at room temperature, transferred into 50 mL Teflon-lined stainless-steel autoclave, and placed in a hot-air oven at 150 ºC temperature for 12 h. A dark brown colour material was obtained, which was washed by ethanol and distilled water several times and dried in a vacuum oven at 60 ºC for 4h. In the mixture of H2O-ethanol (10 mL/40 mL, V/V), 1.5 mL ammonia, and 0.4 mL triethoxy vinyl-silane were dissolved, followed by addition of 0.2 g ZnFe2O4 NPs. The mixture was put under vigorous mechanical stirring for 24 h at 60 ºC. The final product (vinyl silane-modified ZnFe2O4 NPs) was separated by using a simple magnet, washed with ethanol, and dried in an oven at 40 ºC for 12 h. In order to anchor, BTPAm onto vinyl silane-modified ZnFe2O4 NPs surface, 0.1 g of as-prepared NPs (in 20 mL toluene) was added in a round bottom flask containing 0.90 mL BTPAm and 1mL TEA (in 6 mL toluene). The whole mixture was stirred for 24 h at room temperature in a nitrogen atmosphere. After completion of the reaction, the prepared solution 6

Journal Pre-proof was precipitated with methanol, and the particles were separated using a simple magnet. The final product (i.e., BTPAm modified ZnFe2O4 NPs) was dried in a vacuum oven at 50 °C. 2.2.3 Synthesis of vinyl silane-modified BiPO4@GO The synthesis of BiPO4@GO was done through a one-pot hydrothermal method. For this, 1 mmol disodium bismuth phosphate and 1 mmol Bi(NO3)3.5H2O were mixed in 45 mL deionized water, followed by drop-wise addition of 0.65 mL dilute nitric acid. The mixture was stirred at room temperature, until a homogeneous solution has been obtained. After that, 0.2 g GO (synthesized via Hummer’s method) was added into the above solution and stirred for 30 min. The mixture was subsequently transferred into the autoclave and placed in a hot

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air oven at 200 ºC for 1 h. The resulting product (BiPO4@GO) was finally washed with water

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and ethanol and dried in an oven at 80 ºC for 10 h.

After that, for vinyl silane modification of resulted nanomaterial, 0.05 g of

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BiPO4@GO was taken in 20 mL ethanol and sonicated for 1 h. To the suspension, 2.0 mL vinyl triethoxy silane (in 10 mL ethanol) was added, and the pH of the solution was

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maintained between 2-3 by the addition of HCl. The whole solution was finally refluxed at 60 ºC for 24 h. The final product (i.e. vinyl silane-modified BiPO4@GO) was washed three

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times with distilled water, and ethanol and dried in an oven at 50 ºC for 12 h. 2.2.4 Synthesis of BiPO4@GO modified ciprofloxacin imprinted magnetic polymer

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Primarily, 0.5 mmol of template (CIP in 0.5 mL DMSO) was mixed with functional monomer, n-vinyl-caprolactum (1mmol in 0.5mL DMSO) in a beaker. In a separate beaker, 2

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mmol of cross-linker (N, N’-methylene bisacrylamide), BTPAm modified ZnFe2O4 NPs (0.02 g), vinyl silane-modified BiPO4@GO (0.02g) were mixed with CuBr (0.1mmol in 0.5 mL DMSO) and N, N’-Bipyridyl (0.1mmol in 0.5 mL DMSO). Both solutions were mixed together, pour in a glass tube, purged with nitrogen gas for 10 minute and closed with cotton plug and Teflon tape. Afterward, it was placed in an oven at 60 ºC for 4 h. The resulting polymer i.e., BiPO4@GO modified ciprofloxacin adduct magnetic polymer, was kept in a vacuum oven, for further use. To prepare the imprinted polymer (BiPO4@GO-MMIPs), template molecule i.e., CIP, was extracted from the resulted adduct polymer. For this, adduct polymer was incubated in 10 mL of 0.1 N HCl (used as extraction solvent) for 30 minutes. The mechanism of the polymerization process is shown in Section S1 and Scheme S1. The role of each component used in this study is also explained in Section S1. For comparative study and determine the selectivity in the prepared CIP-imprinted polymer, a non-imprinted polymer (NIP) was also prepared using a similar procedure, but in the absence of a template, a molecule referred as, BiPO4@GO-MNIPs. 7

Journal Pre-proof 2.3

Detection of CIP using fluorescence study CIP was determined through fluorescence quenching method. For the quantitative

determination of CIP, Fluorescence Spectrophotometer has been used. For the study, 1.0 mg BiPO4@GO-MMIPs was taken in 10 mL of distilled water in which a different concentration of CIP was spiked. The photoluminescence (PL) was recorded before and after the addition of CIP in the BiPO4@GO-MMIPs. The intensity of the PL spectra for BiPO4@GO-MMIPs has been correlated with the concentration of CIP using the Stern-Volmer equation [36]: [(I0/I)-1] = Ksv C

(1)

Where, I0 is the initial PL intensity of BiPO4@GO-MMIPs i.e. without CIP, I is the intensity

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of BiPO4@GO-MMIPs, after spiking with different concentration of CIP, C is a

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concentration of CIP, Ksv = Stern-Volmer quenching constant. The limit of detection (LOD) of the method was calculated by using three times standard deviation (obtained from three

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times blank run) divided by slope of the linear graph between [(I0/I)-1] and CIP concentration.

Fabrication of BiPO4@GO-MMIPs modified pencil graphite electrode and electrochemical detection of CIP

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2.4

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For the qualitative analysis of CIP, BiPO4@GO-MMIPs modified pencil graphite electrode was fabricated using pencil graphite lead. But prior to this, pencil graphite leads

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(0.5 mm HB) were dipped in the 6.0 M nitric acid solution and kept for 10 minutes, then washed with water for another 10 minutes and dried at room temperature. The rods were

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rubbed by soft cotton for 2 to 3 times to remove non-adsorbed moieties, if any, present on the surface. Now, one end of the pencil rod was introduced into a micropipette tip, and another end is left free for electrical connection by copper wire. As fabricated pencil lead with copper wire connection is now referred to as pencil graphite electrode (PGE). The PGE end kept out from the micropipette tip was modified with the polymer by drop coating process. For this, 1.0 mg of adduct polymer was added into 2.0 mL of DMSO solvent dispersed by ultrasonication and dropped coated onto the tip of PGE and dried at room temperature. From adduct modified PGEs, template (i.e. CIP) molecules were extracted using 5.0 mL of extraction solvent (0.1 N HCl) under the dynamic mode, with stirring for 30 minutes. After extraction, the electrodes will be referred to BiPO4@GO-MMIPs modified PGEs. The electrochemical detection of CIP was done through cyclic voltammetry (CV) and square wave stripping voltammetry (SWSV) studies. The CV was actually used to explore the electrochemical behaviour of CIP and modified PGEs. CV runs were recorded in the potential range of -0.2 V to +0.8 V (versus Ag/AgCl) at the scan rate of 10-500 mV s-1, under 8

Journal Pre-proof optimized analytical conditions. However, for quantitative analysis, the SWSV run was carried out in the potential range of +0.6 to +2.2 V (versus Ag/AgCl) at the scan rate of 10 mV s-1, under optimized analytical conditions [frequency = 15 Hz, pulse amplitude = 25 mV pulse width = 50 m s-1, optimisation time = 30s and optimisation potential = +2.0 V]. After recording SWSV runs for standard concentrations of CIP in the linear calibration range, the calibration equation was derived. The limit of detection (LOD) was calculated for CIP by using three times of standard deviation (calculated by three blank runs) divided by slope of the calibration equation [37]. 2.5

Adsorption behaviour of prepared polymer

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In this work, magnetic nanoparticle and GO were used to incorporate better

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adsorption property in the prepared CIP-imprinted polymer material. In order to study their adsorption property, the batch binding adsorption study was also performed at the

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equilibrium condition. For this, 20.0 mg of BiPO4@GO-MMIPs or BiPO4@GO-MNIPs were added into 100 mL solution of the template having a concentration in the range of 50.0-500.0

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mg mL-1 and stirred for 15 minutes. The adsorption capacity (Qe) was calculated by the following equation (2) [38]: )

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(

(2)

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Where Co is the initial concentration of CIP (mg ml-1), Ce is the concentration of CIP in the supernatant at adsorption equilibrium, V is the volume of template solution, and w represents

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the weight of polymers (g).

Photocatalytic activity of the prepared polymer The photocatalytic properties of BiPO4@GO-MMIPs and BiPO4@GO-MNIPs were

also observed by studying the photo-decomposition of CIP using UV-visible spectroscopy. For this, 20.0 mg of BiPO4@GO-MMIPs or BiPO4@GO-MNIPs was added into the CIP solution (10.0 mg mL-1) and stirred for 20 minutes, in the dark compartment (in the absence of light source to ensure the adsorption equilibrium between polymer and CIP). After that, the solutions along with polymers were kept in UV-chamber to observe the photocatalytic properties of polymers. At different time intervals, the aliquots of the solution were taken, the polymer was centrifuged, and the template was extracted. The extracted solution was run on a UV-visible spectrophotometer and measured at the wavelength of 276 nm. The percentage of the residual compound was calculated by the following equation [38]: η=

(3)

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Journal Pre-proof Here, C is the concentration of CIP after time t (minutes), and C0 is the initial concentration of CIP. 3.

Result and discussion

3.1

Compositional study and magnetic characterization of prepared nanomaterials To evaluate the composition of prepared nanomaterials [ZnFe2O4 NPs, Bi(PO4)@GO,

and BiPO4@GO-MMIPs], XRD study was performed and shown in Figure 1. As shown in Figure 1A, ZnFe2O4 NPs have shown characteristic peaks at 29.86º, 35.34º, 42.72º, 53°, 56.47º, and 62.55º, which corresponds to the (220), (311), (400), (422) (511), and (440) planes of cubic-structured ZnFe2O4 NPs (JCPDS No. 22-101) [39]. The XRD pattern of

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Bi(PO4)@GO is shown in Figure 1B. The strong diffraction peaks were found at 14.45º,

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29.38º 19.98º, 25.36º, 31.23º, 37.77º, 41.79º, 48.67º, 52.02º, and 69.12º which corresponds to the diffraction plane (013) (120), (002), (011), (012), (220), (103), (032), (132) and (340) of

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monoclinic phase structure (JCPDS No. 89-0287). Surprisingly, no diffraction peaks for GO were observed in the prepared Bi(PO4)@GO nanomaterials, which might be possible due to

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the low diffraction intensity of GO in the nanomaterials [40]. Using the Scherrer’s equation (D=kλ/βcosθ), the size of Bi(PO4)@GO nanocomposite is calculated [41]. In the equation, D

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is the size of the nanocomposite, k is the Scherrer’s constant (i.e., 0.94), λ is the X-rays wavelength (0.154 nm for CuKα radiation), β is the full width at half maximum (FWHM) of

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diffraction peak (radian), and θ is the diffraction angle of X-rays. The size distribution of Bi(PO4)@GO nanocomposite was calculated for different peaks with diffraction planes:

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(013) (120), (002), (011), (012), (220), (103), and (032) and found the size (nm) range of nanocomposite as 45, 50, 45.31, 43.94, 42.65, 41.42, 38.15, and 34.52 nm [41]. The calculation gives an idea of size distribution of nanocomposite in the range of 35-50 nm. However, when the XRD study was performed for BiPO4@GO-MMIPs, the peaks of individual nanomaterials are clearly found (Figure 1C). Herein, the broad peaks in the 15-35° suggest the attachment of the polymer layer to the nanomaterial surface. However, the appearance of the peak at 26° confirms the presence of GO in the polymer [42]. In order to evaluate the magnetic properties of prepared the polymer VSM study was performed at room temperature. The magnetization curves obtained for MMIPs and BTPAm modified ZnFe2O4 NPs were shown in Figure S1. The saturation magnetization (Ms) value of ZnFe2O4 NPs and MMIPs were found as 0.94 and 0.099 emu g-1, respectively. The decrease in the magnetization of prepared MMIPs can be attributed to the polymer coating onto the surface of ZnFe2O4 NPs. The result also indicates that MMIPs can be easily separated from aqueous solutions using the external magnet. Figure S2 showed the re-dispersion and 10

Journal Pre-proof separation of MMIPs, in the presence and absence of magnet. In the absence of an external magnetic field, black coloured solid is homogeneously dispersed in the solution. However, when the magnet was applied to the wall of the glass vial, the solid get collected to the side of vial and dispersion become clear and transparent. The whole study confirms the good magnetic property of prepared MMIPs. 3.2

Functional group analysis The presence of functional groups at the surface of nanomaterials and binding

interaction of template with polymer was studied by FT-IR study (Figure 1, D to F). Firstly, the FT-IR spectra were recorded for ZnFe2O4 nanoparticle, before and after their

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functionalization with silane groups. As shown in Figure 1D, ZnFe2O4 nanoparticle showed a

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characteristic peak at 556 cm-1 corresponds to the Fe–O stretching mode and represents the spinel ferrite structure of ZnFe2O4 NPs (Curve a). After modification with vinyl silane, the

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characteristic Si-O-Si peak was observed in the FT-IR spectrum of vinyl modified ZnFe2O4 NPs at 1058 cm-1 (Curve b). After the final modification with BTPAm, the strong peaks were

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observed at 1637 cm-1 -(NH-CO), 1537 cm-1 (-NH), and 697 cm-1 (C-Br), which confirmed the successful synthesis of BTPAm modified ZnFe2O4 NPs (Curve c).

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Similarly, the presence of functional groups at the surface of Bi(PO4)@GO and vinyl silane modified BiPO4@GO was also analysed and shown in Figure 1E. In graphene oxide,

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the absorption band at 3397, 1720, 1620, 1209, 1050, and 857 cm-1 are present corresponds to the presence of –OH, C=O, C=C, -OH, C-O, and –CH groups (Curve a). However, the

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Bi(PO4)@GO nanomaterial shows some extra peaks at 1394, 1008, and 581 cm-1, for C-C (ring), (PO4) and (PO4) and confirmed the successful synthesis of Bi(PO4)@GO (Curve b). After modification with vinyl silane, appearance of extra peaks at 1318 and 773 cm-1 for Si-O-Si and CH (bend) revealed that vinyl silane group has been anchored on the surface of Bi(PO4)@GO (Curve c). The binding interaction between polymer and template molecule was also studied by recording the FT-IR spectra and shown in Figure 1F. Here, curve a, b and c represent the FTIR spectrum for the template, adduct, and imprinted polymers, respectively. As depicted, the template showed absorption bands at 3431, 3045, 2844, 1612, 1478, 1368, 1293 and 1141 cm-1 for -OH, -CH2, -CH3, -CH2 (ring), -OH (bend) and -F functionalities present in the molecule (Curve a). As expected, all these peaks were found in the FT-IR spectrum of adduct polymer also, along with some extra peaks corresponds to the polymer backbone i.e. 1016, 841, 722, and 547 cm-1 for (PO4), -NH, -CH and Fe-O, respectively (Curve b). After

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Journal Pre-proof template extraction, all the peaks representative of template presence in the adduct polymer get disappeared in the FT-IR spectrum of imprinted polymer (Curve c). The study clearly suggests the binding of the template with polymer matrix as well as their complete extraction from the imprinted polymer. 3.3

Morphological study of prepared nanomaterials and polymers The morphological structure of ZnFe2O4 NPs, GO, silane-modified Bi(PO4)@GO,

adduct, and MIP were analysed by field emission-scanning electronic microscopy (FE-SEM) and shown in Figure 2. The spherical and homogenous distribution of ZnFe2O4 NPs is clearly visible in the FE-SEM image (Figure 2 A and B). The particle size is found to be in the range

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of ~30 nm. In Figure 2 C and D, the sheet-like morphology of GO is clearly visible.

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However, after modification with BiPO4, the sheet like morphology of GO gets converted to the rod-shaped BiPO4@GO (Figure 2 E). The rod shape BiPO4@GO possesses a sharp edge

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with a size of ~200 nm (Figure 2 F). In contrast to these nanomaterials, the adduct polymer has a plane and close-packed structure with no noticeable pore (Figure 2 G). However, after

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extraction of template i.e. imprinted polymer exhibited an irregular and rough surface (Figure 2 H and I). It has distinctly visible pores, which might be generated after the extraction of the

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template molecule from the adduct polymer matrix. FE-SEM study of non-imprinted polymer (i.e. BiPO4@GO-MNIPs) was also performed and shown in the Figure S3, A and B. As

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shown in figure, BiPO4@GO-MNIPs surface contains, sheets of graphene, spherical-shaped nanoparticles but does not possess any compact structure with pore like-morphology. It

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confirms that BiPO4@GO-MNIPs does not contain any imprinting site. To further evaluate the morphology of prepared samples, their TEM analysis was also performed and shown in Figure 3 and 4. Similar to the FE-SEM image, the ZnFe2O4 NPs shows spherical morphology which has a size in between 4.27-6.37 nm (Figure 3, A-D). The sheet-like morphology of GO is also clearly visible in their TEM images, shown in Figure 3 (E-H). Exactly matching with the FE-SEM results, the silane-modified Bi(PO4)@GO shows very good rod-shaped morphology with clear edges and sharp boundaries. A single rod has a length of 319.57 nm and a width of 34.14 nm (Figure 4, A-C). Afterward, the TEM image of the adduct polymer was recorded and shown in Figure 4 (D and E). It is a compact and amorphous structure with no clear visible structures. However, unlike this, the BiPO4@GOMMIPs have small particle-like morphology, which may be occurred due to the cavities present in the polymer (Figure 4, F-H).

12

Journal Pre-proof 3.4

Fluorescence detection of CIP In order to explore the fluorescence behaviour of prepared BiPO4@GO-MMIPs, CIP

detection was performed by fluorescence spectroscopy also. For this experiment, different concentration of CIP was spiked in BiPO4@GO-MMIPs, and change in fluorescence intensity was observed. The camera picture of the BiPO4@GO-MMIPs in the absence and presence of CIP is also recorded in the UV-chamber (Figure S4). As expected, with CIP spike in the polymer, fluorescence quenching occurred, and fluorescence intensity of polymer gets decreased (Figure 5A and Figure S4). BiPO4 is a wide band gap photocatalyst, made up of O 2p, Bi 6s, P 3s and P 3p as valence band and Bi 6p as conduction band [43]. Under the

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excitation of 360 nm wavelength, the blue emission was recorded at 450 nm. According to Xue et al. the emission band observed from BiPO4 can be attributed to the 3P1-1S0 transitions

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of Bi3+ [44]. They also suggested that fluorescence of the BiPO4 material, also depends upon

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their morphological variation. Herein, the rod-shape of BiPO4 nanoparticle can also be attributed to the good fluorescence property of prepare nanomaterial. However, when CIP is

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added in the polymer, the transition gets inhibited and results in quenching of fluorescence intensity.

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The change in fluorescence intensity was plotted against the concentration of CIP, and a good linear regression plot has been obtained in the range of 39.0 μg L-1 to 328.0 μg L-1.

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The linear calibration equation can be represented as [(I0– I)/I] = (0.0032 ± 5.36×10-5) × C + (0.020 ± 0.084), n=11, R2=0.99, where I0 and I is intensity of BiPO4@GO-MMIPs in the

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absence of CIP and with different concentration of CIP, respectively (Figure S5). The LOD for the method is calculated to be 0.4 μg L-1. In addition to this, for comparison, the performance of BiPO4@GO-MNIPs has also been evaluated towards detection of CIP. The PL spectra recorded for BiPO4@GO-MNIPs is shown in Figure S6-A. The change in fluorescence study is not found to be much linear (R2 = 0.88) and shows the performance in very limited concertation range i.e. from 99-291 μg L-1. The linear equation for BiPO4@GOMNIPs is: [(I0-I)/I] = (0.002 ± 0.0005) × C + (-0.252 ± 0.113), n=5, R2=0.88. 3.5

Electrochemical activity of fabricated PGEs Prior to studying the electrochemical behaviour of modified PGEs towards CIP

detection, electrochemical activity of fabricated PGEs was also examined by cyclic voltammetry technique using potassium Ferrocyanide as an electroactive probe molecule. For this, CV runs for ZnFe2O4 NPs, BiPO4@GO, MIP, NIP, and un-modified PGEs were recorded in the 0.1 M potassium ferrocyanide solution (Figure 5B). On all the electrodes, the redox behaviour of [Fe(CN)6]3-/4- is clearly visible, but significant change in current was 13

Journal Pre-proof observed on each electrode. The MIP-modified PGE showed the highest current response, while bare PGE showed the lowest current. As shown in the figure, BiPO4@GO shows a better current response in comparison to the ZnFe2O4 NPs. Graphene oxide (GO) has a sheet-like structure that provides a platform for the growth of the sharp edge structure of Bi(PO4) nanocomposite. In which the negatively charged GO surface has interacted with positively charged Bi+2 ion via electrostatic attraction. As a result, all bismuth ion gets adsorbed on the surface of GO to form a loosely bound GO-Bi+2 complex. It might be possible that due to this process, the nanocomposite of Bi and GO is converted into a rode shape structure [45]. This can also be the reason for the

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higher CV current response of BiPO4@GO than ZnFe2O4 NPs, owing to an increase in the

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modulation of conductance of channel and increasing the potential barrier formed at Bi(PO4)@GO nanocomposite interface [46]. However, while the same ZnFe2O4 NPs and

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BiPO4@GO get incorporated in the polymer matrix, the enhanced current response was observed, owing to their synergetic properties as well as the presence of imprinted cavities in

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the BiPO4@GO-MMIPs. The change in current behaviour can also be attributed to the presence of imprinted cavities in the MIP-PGEs, which is missing in bare or NIP-PGEs,

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provided space for the analyte (ferrocyanide) to be transported onto the electrode surface. In the absence of such cavities, bare and NIP-modified PGEs showed a lower current response.

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An increase in current on NIP-PGE in comparison to the bare PGEs can be attributed to the

PGE. 3.6

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presence of GO nanomaterials, which may improve the electrochemical performance of NIP-

Electrochemical behaviour of CIP on BiPO4@GO-MMIPs-PGEs The electrochemical behaviour of CIP (157.0 g L-1) was investigated by cyclic

voltammetry analysis at a different scan rate of 0.1 to 0.5 V s-1 in the potential range of +2.5 to -0.2V in phosphate buffer solution (PBS). As shown in Figure 5C, at all the scan rates, a single peak was obtained at +1.6 V in the anodic run and no cathodic peak was observed in the reverse scan, which suggests the irreversible electrochemical oxidation of CIP. The oxidation mechanism of CIP is shown in Scheme S3, in which two electrons have been accepted by the –NH group of CIP molecule, and converted into -N-OH group in aqueous medium [47]. In addition, a linear relationship was obtained between the CV peak current (Ip) and scan rate (). The linear relationship between anodic peak current and the scan rate was depicted by following equation: Ip (μA) = (421 ± 14.36) + (387.7 ± 4.76), n = 5, R2 = 99

14

Journal Pre-proof (Figure S7). The anodic peaks increase linearly with the scan rate, which confirms that electrochemical oxidation of CIP has followed adsorption-controlled kinetics. 3.7

Quantitative detection of CIP by square wave stripping voltammetry (SWSV) Square wave stripping voltammetry (SWSV) has high sensitivity in electrochemical

experiments. Therefore, quantitative detection of CIP was done through the SWSV study. For this, the effect of CIP concentration on the SWSV current response was recorded under the optimized experimental conditions (Figure S8 and Section S2). The SWSV runs were recorded for various concentrations of CIP in the potential window of +1.0 to +1.8 V. The oxidation peak current (Ipa) increased with an increase in the concentration of CIP in the

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concentration range of 39.0 g L-1 to 740.0 g L-1 and shown in Figure 5D. Afterward, the current becomes constant owing to the saturation of binding sites present at the imprinted

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polymer-modified PGE. The calibration equation calculated for CIP is: Ipa (μA) = (0.1295 ±

-p

0.0053) × C + (231.97 ± 2.403), n= 9, R2 = 0.988 (Figure S9). The limit of detection (LOD) and limit of quantification (LOQ) were also calculated using the slope of this calibration

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equation and found to be 0.12 μg L-1 (S/N=3) and 0.39 μg L-1 (S/N=10), respectively.

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In addition to this, for comparison, the performance of BiPO4@GO-MNIPs has also been evaluated towards the detection of CIP. The SWSV runs recorded for BiPO4@GOMNIPs is shown in Figure S6-B. The increase in current with respect to an increase in the

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concentration of CIP is not found to be much linear (R2 = 0.95) and shows the performance in very limited concertation range i.e., from 99-654 μg L-1. The linear equation for BiPO4@GO-

3.8

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MNIPs is: Ipa (μA) = (0.170 ± 0.016) × C + (91.874 ± 7.102), n= 7, R2=0.95. Investigation of Adsorption behaviour of polymers After the quantitative detection of CIP by electrochemical and fluorescence study, the adsorption behaviour of polymers towards CIP was also studied, which can be used for the removal of CIP from real samples. For this, the adsorption capacity of BiPO4@GO-MMIPs and BiPO4@GO-MNIPs were calculated using different concentrations of CIP (50-500 mg mL-1) and shown in Figure 5E. As depicted, with an increase in the concentration of CIP, the adsorption capacity of imprinted polymer also increased and became constant beyond 400 mg mL-1 concentration of CIP. However, contrary to this behaviour, the adsorption capacity of NIPs gets increasing with the increase in the concentration of CIP, although the adsorption capacity is very low in comparison with imprinted polymer. Imprinting factor (IF= QMIP/QNIP) was also calculated for this study and shown in Figure 5E. The difference in adsorption behaviour of BiPO4@GO-MMIPs and BiPO4@GO-MNIPs and high imprinting

15

Journal Pre-proof factor can be attributed to the presence or absence of imprinting cavities at the surface of polymers. Imprinted polymers showed high adsorption capacity than the NIP owing to the presence of cavities on their surface, which is suitable to the size and shape of the CIP molecule and promotes its binding with the polymer matrix. On the other hand, NIP has no cavities on their surface, so the adsorption of template molecule is a kind of non-specific adsorption on the surface of the polymer, which goes on increasing with an increase in template concentration and can be easily removed by simple water washing. The high adsorption capacity of the BiPO4@GO-MMIPs clearly suggests that prepared polymer can be successfully used for the removal of CIP from real samples.

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Adsorption kinetics is one of the important studies to explain the efficiency of

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adsorption and determining the saturation time. Herein, the adsorption kinetics study was performed using both types of polymers i.e., BiPO4@GO-MMIPs and BiPO4@GO-MNIPs.

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As expected, it was found that the adsorption amount of CIP on MIP/NIP was increasing with the increase in time (recorded in minutes). However, the adsorption is faster in MIP than NIP.

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The adsorption of CIP is fast in initial time i.e., 5 to 25 minutes and after that slowdown, which indicates that adsorption equilibrium was achieved. At the equilibrium, the imprinting

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sites of the polymer was fully occupied by CIP. Although the BiPO4@GO-MMIPs and BiPO4@GO-MNIPs were shown similar adsorption amount of CIP, MIP has adsorbed more

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CIP than NIP, because it had a lot of imprinting sites for CIP, But NIP has no imprinting sites.

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Adsorption kinetic studies were carried with a known amount of CIP (200 mg L-1) with 20 mg polymers (BiPO4@GO-MMIPs and BiPO4@GO-MNIPs). The pseudo-first-order and pseudo-second-order models were used for the analysis of kinetic adsorption data using the following equations [48]:

log (Qe- Qt) = log Qe –K1 t/2.303

(4)

t/Qt = 1/K2 Qe2 + t/qe

(5)

Here, Qe and Qt are the adsorption capacity at equilibrium and at time t, respectively (mg g-1); K1 is the pseudo-first-order rate constant (min-1), and K2 is the pseudo-second-order rate constant (g mg-1 min-1). The constants used in the kinetic model are listed in Table S1. Compared with the two kinetic formulas, the R2 value of the pseudo-first-order kinetic model is closer to 1 than the pseudo-second-order model, and it seems that the pseudo-first-order model can better fit the adsorption process. Similarly, the Qe calculated by the pseudosecond-order model is closer to the Qe,exp value (i.e., 252 mg g-1 for MIP and 27 mg g-1 for

16

Journal Pre-proof NIP, Figure 5E) obtained from the experiment, which further proves that both the adsorption of CIP by MIPs and NIPs are in accordance with pseudo-second-order kinetic model. 3.9

Photocatalytic degradation of CIP As mentioned in the introduction, here, we have tried to develop a complete solution

for detection, removal as well as degradation of CIP. The role of BiPO4@GO-MMIPs towards detection and removal of CIP was already discussed in the previous sections, and for degradation of CIP, the photocatalytic reaction was performed. For this study, the fixed concentration of CIP was incubated with BiPO4@GO-MMIPs and BiPO4@GO-MNIPs in the dark chamber. After some time, the solution was placed in UV-chamber, and their small

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aliquots were studied UV-visible spectroscopy. The decrease in absorbance value with

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increase in time with BiPO4@GO-MMIPs and BiPO4@GO-MNIPs are shown in Figure 6 A and B, respectively. Correspondingly, the concentration of CIP before and after UV-light

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exposure was also calculated and depicted in Figure 6C. As shown in these figures, both MIP and NIPs are capable of doing complete degradation of CIP in a maximum of 80 minutes.

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However, the difference in their performance can be easily understood on the basis of the presence or absence of cavities in the respective polymers.

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The photocatalytic behaviour of Bi(PO4)@GOMMIP and Bi(PO4)@GOMNIP towards CIP degradation can be attributed to the presence of GO and Bi(PO4) [49]. In the

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prepared polymer, having sp3 and sp2 hybridized carbon atom, GO has a less energy gap than Bi(PO4), which has an active absorption spectrum in the visible region. So, during photo-

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degradation of CIP, transfer of an electrons occurs from lowest unoccupied molecular orbital (LUMO) of GO to highest occupied molecular orbital (HOMO) of Bi(PO4) nanocomposite via π to π* transition [50]. By the transfer of electron, a positive hole (H+) was generated, which simultaneously transfers to HOMO of Bi(PO4)@GOMMIP/Bi(PO4)@GOMNIP from valence bond of Bi(PO4) nanocomposite [49, 50]. According to other literatures, BiPO4, as a highly active ultraviolent photo-catalyst, have attracted importance by more and more researchers recently, because of their wide band gap (3.9 eV) [51]. In general, when BiPO4, like semiconductor-based photocatalyst comes under UV-light, holes (h+) and electrons (e−) are generated (Scheme S4). Subsequently, the photon absorbed by the nanomaterial and electrons exited from valence band (VB) to conduction band (CB), if the energy of photons is equal or more than the band gap (Eg) and leaves holes in the VB [52]. Afterward, the photon generated electrons and holes start forming superoxide (O2−•) and hydroxyl (•OH) radicals. During the photo-degradation of CIP, the •OH and O2−• radicals are the primary oxidants. The •OH, O2−•, and •OOH radicals attack 17

Journal Pre-proof the CIP, which results in several intermediates. The resultant intermediates subsequently react and finally degraded to the CO2 and H2O like final products (Scheme S4) [52]. 3.10

Selectivity study The selectivity of imprinted polymer for CIP was studied in the presence of some

interference compounds, which have a similar structure to the CIP or commonly present in the biological samples. The interfering compounds such as adenine, arginine, ascorbic acid, cysteine, uric acid, L-pyro glutamic acid, Indol-3-acetic acid were analysed under the optimised analytical condition to discover the selectivity of the proposed MIP-sensor. The corresponding results were displayed in Figure 5F. It is very clear in the figure that the

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proposed MIP-sensor showed some current response for these interfering compounds, which

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could be attributed to their non-specific adsorption at the electrode surface. For the same reason, NIP-sensor also showed some of the currents for some of the interfering compounds.

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The theory can be proved, after recording the SWSV current on the same NIP electrode, after simply washing the electrode by distilled water. The negligible current response was

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observed after washing the electrode in the presence of interfering compounds. However, under similar condition, even in the presence of interfering compounds, when CIP is spiked

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(MIP-spike, Figure 5F), the MIP-electrode showed very high current response for CIP, which suggested that proposed sensor has only selective recognition capacity for the CIP molecule,

3.11

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even in the presence of a various type of interferent compounds. Real sample analysis and comparative study

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The collected samples (whole blood, serum, and milk) from a government hospital and local milkman were examined by the SWSV technique for practical application. Firstly, the human serum, whole blood, and milk were diluted with pH 7 PBS solution (10 mL). Standard calibration equation was plotted in all the kind of real sample and shown in Table S2. The SWSV technique was used to detect the known concentration of CIP in the real samples by the standard addition method. Additionally, recovery and relative standard deviation (RSD) was also calculated and shown in Table 1. The SWSV runs recorded for real sample analysis was depicted in Figure 6 (D to F). AS shown in Figure and Table 1, the average recovery range and relative standard deviation (RSD %) were found to be in the range of 98 to 100 % and 1.1 to 1.4 %, respectively. The good recovery and low RSD values with good SWSV response clearly suggest the practical or real-time application of proposed sensor towards CIP detection. This study also suggested that the proposed sensor is able to identify and quantify the template molecule in complex matrices also. 18

Journal Pre-proof The comparison of the different parameters (linear range, LOD and recovery) between the proposed sensor, and previously reported sensors has been made and portrayed in Table 2 [1, 53-67]. In comparison to the earlier reported methods, the proposed sensor has exhibited better sensitivity and selectivity along with a good linear range and very low LOD value for the detection of CIP. In addition, contrary to all these reported methods, our material can be successfully used for not only removal but the degradation of CIP also. 3.12

Stability, reusability, and reproducibility of BiPO4@GO-MMIPs modified PGEs To examine the reproducibility of prepared sensor SWSV runs were recorded for

196.0 μg L-1 of CIP for six times. The RSD value was obtained as 1.2% for the repetitive

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analysis. Similarly, to explore the reproducibility of the results, a set of ten PGEs were

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prepared and used for determination of the fixed concentration of CIP i.e., 157 μg L-1. The RSD was calculated for this study also and found to be 1.2%. To explore the storage stability

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of the prepared sensor, the fabricated electrodes were stored at room temperature for 30 days. The current response was recorded after storage of 30 days, and 99.4% current response was

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obtained for a fixed concentration of CIP. Additionally, the same sensor was used 50 times repeatedly under the same experimental situation, and no change in their current response

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was recorded. The overall study clearly suggests the good repeatability, high stability,

sensor-based study. 4.

Conclusion

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reproducibility, and reusability of the proposed sensor, which are the key parameters of any

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In summary, CIP-imprinted polymer was successfully synthesized by atom transfer radical polymerisation (ATRP) process using BiPO4@GO as photocatalyst unit, ZnFe2O4 as magnetic nanoparticles, imprinted polymer as selectivity unit. Using the BiPO4@GOMMIPs, we have successfully detected a trace level of CIP in complex matrices like blood and milk. In addition, using the magnetic feature of prepared polymer, their fast and easy removal was also achieved with high adsorption capacity. Contrary to earlier reported methods for CIP detection, herein, we have not the only separation/removed or detected the template molecule, but degraded it completely using safe and easy photocatalytic degradation method. The proposed MIP-based sensor showed high selectivity and specificity towards CIP, even in the presence of similar and biologically co-existing interfering compounds. The fabricated sensor has shown good selectivity, specificity, sensitivity, utility, simplicity, rapidity, sensitivity, low cost, and stability for the determination of CIP. The present working mode of action i.e., selective removal, detection, and subsequent degradation, can open a new

19

Journal Pre-proof platform for the fabrication of imprinted polymer with catalytic activities, which rarely reported in the field of molecular imprinting technology. Acknowledgment Authors are thankful to DST for sponsoring the research project to R.M. (Ref. No.: SERB/F/2798/2016-17). The experimental work has been carried out by Mr. S. Kumar and he is responsible for all the data presented in this work. Reference 1. P. Gayen, B. P. Chaplin, Selective Electrochemical Detection of Ciprofloxacin with a Porous Nafion/Multiwalled Carbon Nanotube Composite Film Electrode, ACS Appl.

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Journal Pre-proof Figure caption Scheme 1: Schematic illustration for preparation of BiPO4@GO-MMIPs. Figure 1: XRD pattern of (A) ZnFe2O4 NPs, (B) Bi(PO4)@GO, (C) BiPO4@GO-MMIPs. FT-IR study of (D) ZnFe2O4 NPs ((curve a), vinyl modified ZnFe2O4 NPs (curve b), BTPAm modified ZnFe2O4 NPs (curve c). FT-IR study of (E) GO (curve a), Bi(PO4)@GO (curve b) vinyl silane modified Bi(PO4)@GO (curve c). FT-IR study of (F) ciprofloxacin (curve a) Adduct polymer (curve b) MIP (curve c).

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Figure 2: The FE-SEM image of (A and B) ZnFe2O4 NPs, (C and D) GO, (E) The rod-

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shaped BiPO4@GO, (F) The sharp edge BiPO4@GO, (G) Adduct polymer (H and I) MIP.

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Figure 3: TEM and SAED images of ZnFe2O4 NPs (A to D) and GO (E to H).

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Figure 4: TEM and SAED images of (A to C) silane-modified Bi(PO4)@GO, (D-E) Adduct

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polymer, and (F to H) MIP.

Figure 5: (A) Fluorescence spectra of CIP at different concentrations (a-g) 39.0 μg L-1 to

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328.0 μg L-1, (B) Cyclic voltammograms for different electrodes as Bare PGE, ZnFe2O4PGE, BiPO4@GO-PGE, NIP-PGE, MIP-PGE, (C) Cyclic voltammograms of CIP at different

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scan rate (0.1 – 0.5 V s-1), (D) Square wave stripping voltammograms obtained for CIP in range of (a-j) 39 to 740 μg L-1, (E) Binding adsorption isotherm for BiPO4@GO-MMIPs and BiPO4@GO-MNIPs with imprinting factor, (F) Effects of various interferents on the detection of CIP.

Figure 6: UV-visible spectra of BiPO4@GO-MMIPs (A) and BiPO4@GO-MNIPs (B), (C) Photo degradation of CIP catalysed by BiPO4@GO-MMIPs and BiPO4@GO-MNIPs under UV radiation. The real sample analysis of (D) Blood (E) Serum (F) Milk.

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Journal Pre-proof Table 1: The determination of CIP in some real samples by BiPO4@GO-MMIPs. S.N.

Sample Added

1.

Analyte (μg

Whole Blood

2.

Serum

Milk

Recovery (%)

R.S.D (%)

38.2 ± 0.45

98

1.2

67.0

66.3 ± 0.86

99

1.3

39.0

38.6 ± 0.54

99

1.4

68.0

68.0 ± 0.88

100

1.3

39.0

38.49 ± 0.46

98.7

1.2

67.5

67.16 ± 0.94

99.5

1.4

-1

L )

(μg L )

39.0

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3.

Determined Value

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Table 2: Comparison between various previously reported method for detection of CIP and our

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work.

Linear range

Name of sensor

1.

DPV

Porous-Nafion-MWCNT/BDD 1.6–16.5

2.

CV/DPV

MMWCNTs@MIP/CPE

1.6–281.63

3.

CV/SWV

AuNP/CHI/SPE

4.

DPV

5.

EIS

6.

SWV

7.

CV/DPV

8.

CV

9.

DPV

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S.N. Technique

(g/L)

LOD (g/L)Recovery (%) Ref. -

1

0.56

97.6–102.5

53

33.33 - 49701 0.33

97.2 –99.3

54

PEI@Fe3O4@CNTs

9.9 – 23193.8 0.99

97 –108

55

g-CN/BiOCl-modified ITO

0.5 - 1840

90.5–112.6

56

NiONPs–GO–CTS:EPH/GCE 13.21–321.39 1.98

93–108

57

PAR/EGR/GCE

13.25–39760 3.3

97.8–105.4

58

Glassy carbon electrodes

9940–99402 0.46

96

59

CPE/CNP-NH3+/SDS-

165–3313

99.85–101.5 60

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1.6

0.2

1.6

10. Fluorescence BSA-AuNCs

132.53–165.670.99

98.69–99.55 61

11. Fluorescence MPA-CDS

4.30–49701

13.25

97.2–103

19–4638.76

19

99.47–103.4 63

12

Fluorescence Terbium (Tb3+)-(CPNPs)

13. Fluorescence LCPNPs

62

331.34–13253.6 258

97.03–104.89 64

3.3–49701

0.66

95.56−104.53 65

15. Fluorescence S-CDs

6.6–331.34

2.21

92.3–102.5

66

16

497.01–49999.2 265.07

94

67

14. Fluorescence

Ratiometric FL of CDs/SiDs conjugates

Fluorescence MIP-based micro-

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Journal Pre-proof mechanical cantilever

17.

SWSV PL

39.0 to BiPO4@GO-MMIPs

740.0 39.0 to 328.0

0.39 0.40

98–100

This work

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CV cyclic voltammetry, DPV differential pulse voltammetry, SWV square wave voltammetry, EIS electrochemical impedance spectroscopy, SWSV square wave stripping voltammetry, PL photoluminescence, MMWCNTs@MIP/CPE magnetic multi-walled carbon nanotube/ carbon paste electrode, MWCNT/BDD multiwalled carbon nanotube/boron doped diamond electrode AuNP/CHI/SPE gold nanoparticls/ chitosan/screen printed electrode, PEI@Fe3O4@CNTs polyethylenimine- magnetite nanoparticle-carbon nanotubs, gCN/BiOCl-modified ITO graphitic carbon nitride/indium tin oxide, NiONPs–GO–CTS: EPH/GCE nickel oxide nanoparticles-graphene oxide- chitosan, epichlorohydrin/glassy carbon electrode, PAR/EGR/GCE poly(alizarin)/electrodeposited graphene/glassy carbon electrode, CPE/CNP-NH3+/SDS carbon paste electrode/carbon nanoparticle3+ ammonium/sodium dodecyl sulphate. Terbium (Tb )-(CPNPs) = terbium (Tb3+)-based coordination polymer nanoparticles, FL of CDs/SiDs = fluorescence of carbon dots/silicon 4 dots. S-CDs = Sulphur-doped carbon dots, BSA-AuNCs = Bovine serum albumin-gold nanoclusters, MPA-CDS = 3-mercaptopropionic acid-cadmium sulphide quantum dots.

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Journal Pre-proof

Credit Author Statement Sunil Kumar: Methodology, Data curation, Writing and Editing, Paramita Karfa: Writing- Original draft preparation, Kartick Chandra Majhi: Software, Validation, Rashmi Madhuri: Conceptualization, Supervision and Reviewing.

Statement of declaration

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“Declaration of interest: none”

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Research Highlight

BiPO4@GO-MMIPs has been successfully synthesized act as photocatalyst.



Prepared MMIP is not only able to remove but degrade the antibiotic drug too.



First time, we have incorporated the Bi(PO4)@GO with magnetic imprinted polymer.



The sensor showed excellent LOD values i.e. 0.39 μg L-1 and 0.40 μg L-1.

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

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Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6