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Rapid and sensitive detection of enrofloxacin hydrochloride based on surface enhanced Raman scattering-active flexible membrane assemblies of Ag nanoparticles
Journal of Environmental Management 249 (2019) 109387
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Journal of Environmental Management journal homepage: www.elsevier.com/locate/jenvman
Research article
Rapid and sensitive detection of enrofloxacin hydrochloride based on surface enhanced Raman scattering-active flexible membrane assemblies of Ag nanoparticles
T
⁎
Hongji Lia,b,c, , Mingchao Wangd, Xiaoxue Shenb, Sui Liub, Yan Wange, Yue Lie, ⁎⁎ Qingwei Wanga,c, , Guangbo Chea,c a
Key Laboratory of Preparation and Applications of Environmental Friendly Materials (Jilin Normal University), Ministry of Education, Changchun, 130103, PR China College of Environmental Science and Engineering, Jilin Normal University, Siping, 136000, PR China Key Laboratory of Functional Materials Physics and Chemistry of the Ministry of Education, Jilin Normal University, Changchun 130103, PR China d College of Physics, Jilin Normal University, Siping, 136000, PR China e College of Chemistry, Jilin Normal University, Siping, 136000, PR China b c
A R T I C LE I N FO
A B S T R A C T
Keywords: Surface enhanced Raman scattering Membrane separation Trace analysis Enrofloxacin hydrochloride
The abuse of antibiotics resulted in the pollution of river is more and more serious and it was necessary to exploit a sensitive detection method to improve the traditional analysis measurement. In this test, it is reported an Agbased SERS sensing membrane synthesized by the technique of SERS detection and membrane separation. SERS analysis technique presented sensitive detection property, which could be applied into trace analysis. Membrane separation could effectively enrich the analytes to improve the sensitivity. The SERS membrane was synthesized by filtrating Ag nanoparticles (NPs) on the surface and investigating the amount of PVP and Ag NPs to the sensitivity. Meanwhile, the addition of Ag NPs effectively improved the hydrophilia to promote the detection effectivity in the water. By the investigations of optical analysis, the SERS membrane presented high sensitivity in the detection of antibiotics. Under the optimal condition, the SERS intensity presented good linear relationship with the concentration of antibiotics between 1.0 nmol L−1 and 200 nmol L−1. This method provided a sensitive detection approach and broadened the investigation field of antibiotics detection.
1. Introduction Antibiotics have been widely applied in human and veterinary medicine depending on the excellent ability of bacteriostasis (Tao et al., 2019; Xie et al., 2017). However, residual antibiotics have been detected in most mammals’ excrement and superfluous antibiotics will affect the normal physiological function of human and other mammals (Kim et al., 2015). Therefore, the detection of antibiotics can make a contribution to the environment protection. Up to now, there are lots of analytical methods have been used into antibiotics detection, such as HPLC, GC-MS, TLC and ELISA (Yu et al., 2019a; Ershadi et al., 20017; Tang et al., 2017; Liu et al., 2016; Ha et al., 2014; Huang et al., 2013). However, the traditional methods contain some areas that need improvement, such as: a) the testing process is expensive; b) the process of sample pretreatment is complex; c) the consumption of testing sample is
numerous. Therefore, it is imminently to develop a novel method which could more effectively detect the residual antibiotics. In order to realize the ultratrace sample detection, the surface enhanced Raman scattering (SERS) technology is gradually attracting to the view of scientists. Nowadays, as an ultrasensitive detection method, SERS has been applied into most compounds analysis, such as: organic pollutants, metal ions, endocrine disrupter et al. (Li et al., 2017a, 2018a; Zhou et al., 2017; Fang et al., 2013). Comparing to the traditional analysis approach, SERS technique possesses the merits such as: less analysis dosage, short test time and good repeatability. Though the SERS is a sensitive detection technology, the synthesis of substrates is very rigorous. In order to get more sensitive SERS property, the substrates should possess several targets, such as: a) rough surface morphology; b) regular structures; c) easy to repeat (Li et al., 2017b; Chaunchaiyakul et al., 2017; Huy et al., 2017; Wang et al., 2017). Based
⁎ Corresponding author. Key Laboratory of Preparation and Applications of Environmental Friendly Materials (Jilin Normal University), Ministry of Education, Changchun, 130103, PR China. ⁎⁎ Corresponding author. Key Laboratory of Functional Materials Physics and Chemistry of the Ministry of Education, Jilin Normal University, Changchun 130103, PR China. E-mail addresses: [email protected] (H. Li), [email protected] (Q. Wang).
https://doi.org/10.1016/j.jenvman.2019.109387 Received 22 April 2019; Received in revised form 23 July 2019; Accepted 10 August 2019 0301-4797/ © 2019 Elsevier Ltd. All rights reserved.
Journal of Environmental Management 249 (2019) 109387
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on the considerations, the Ag-based substrates become the first choice of SERS substrate preparation for the characteristics of significant enhancement property, easy preparation and excellent reproducibility (Tao et al., 2016; Gao et al., 2017). Furthermore, it has been widely accept that the SERS signal of the template molecules can be enhanced 6–8 orders when they are adsorbed in the gaps named “hot spots” of Ag NPs (Nie and Emory, 1997; Xinne et al., 2015). Importantly, the greater advantage of SERS detection is that this method doesn't affect by the state of the samples. It can be directly detected and doesn't affect by the residual solvent. However, the SERS substrates of the past are mainly focused on the powders synthesis, which neglects the disadvantage of difficult to recycle. Therefore, it is necessary that develop a synthesis technology to guarantee the effect of sensitive detection and recycle, simultaneously. In recent years, the technology of membrane separation has attracted more and more attention for the superior properties, such as: large surface to volume ratio, excellent flexibility, easy installation, and low cost (Saidi, 2017; Ahmad and Ramli, 2013; Stoquart et al., 2012). Among varies membranes, poly(vinylidene fluoride) (PVDF) presents promising properties due to its peculiar antioxidation activity, excellent chemical resistance, thermal stability, and good membrane-forming properties (Wang et al., 2012; Chiang et al., 2009; Lee et al., 2013). Based on these encouraging properties, it is considered that introduce the technology of membrane separation into the SERS detection to improve the deficiencies. The PVDF membrane exhibits lots of excellent properties, but this material own a serious disadvantage in the antibiotics detection which is hydrophobic nature. Thanks to the nature of hydrophilia and fouling resistance, the modification of Ag NPs not only can supply the property of SERS detection but also can improve the hydrophilia and fouling resistance properties of PVDF membrane, which can effectively increase the cycle times. Herein, it is reported that an Ag-based SERS membrane analysis system for the detection of enrofloxacin hydrochloride (EH) in water. In this investigation, the flower-like Ag NPs are firstly synthesized to make the SERS substrates get more “hot spots”. Then the Ag NPs are fabricated on the PVDF membrane by filtration to prepare the Ag-based PVDF membrane (APM) and the optimal dosage of Ag colloid was also studied to ensure getting the most sensitive APM. This mehod presented a novel analysis measurement which combined SERS technique and membrane separation. It could effectively increase the attachment area and promote the detection sensitivity. Meanwhile, the addition of Ag NPs improved the hydrophilia, which promoted the recycle detection times of APM. Moreover, the morphology, performance and sensitivity were also investigated and it was proved from the results that this APM could be applied into the EH detection in the water.
purchased from Sinopharm Chemical Reagent Co.,Ltd. (Shanghai, China). Doubly distilled water was used in all cleaning processes and aqueous solutions. 2.2. Apparatus and measurements Surface morphology of the samples was analyzed with a scanning electron microscope (SEM, JSM-7800F, JEOL, Japan). Infrared spectra (4000-400 cm−1) were collected on a FT-IR apparatus (Frontier, PE, U.S.A.). X-ray diffraction (XRD) spectra were collected on a X-ray diffractometer (PC2500, RIGAKU, Japan) with Cu Ka radiation over the 2θ range of 30-80°. Raman spectra were obtained by a confocal microRaman spectroscopy system (SENTERRA II, Bruker, Germany). 2.3. Synthesis of flower-like Ag NPs The flower-like Ag NPs were synthesized as follows: 170 mg AgNO3 solution and 1.92 g citric acid were dispersed into 60 mL distilled water. Then 500 mg ascorbic acid was added into the mixture system under stirring. After 1.0 h, the black precipitate was gathered by centrifugation and dried in vacuum. 2.4. Fabrication of APM Firstly, the PVDF membrane was synthesized by the method of nonsolvent induced phase separation (NIPS): 4.0 g PVDF powder was dispersed into 20 mL DMAc and the system was stirred under room temperature. Subsequently, a certain amount of PVP powder was added and continued stirring 24 h. Then the solution was placed 12 h for exhausting the mixture gas and casted the PVDF membrane on a clean glass plate. The glass plate was immersed into water and accomplished the procedure of phase inversion to obtain the PVDF membrane. Secondly, the flower-like Ag NPs were assembled on the surface of PVDF membrane by suction filtration: a certain amount of Ag dispersion liquid was dropped on the surface of PVDF membrane and the solution was carried out suction filtration under the pressure of 0.1 Mpa. 2.5. Raman detection measurement The SERS detection capability of APM was reflected by Raman detection. In this experiment, all the Raman detections were under the uniform conditions: the excitation was 532 nm. The spectra of each sample were collected with an exposure time of 10 s and incident laser power of 0.25 mW. SERS spectra were collected using a 50 × Nikon objective.
2. Experiment section 3. Results and discussion 2.1. Chemicals and materials 3.1. Procedure of APM synthesis Enrofloxacin hydrochloride (EH) was purchased from National Institutes for Food and Drug Control. PVDF powder was purchased from French company Arkema. Polyvinylpyrrolidone (PVP, k30), citric acid, ascorbic acid were purchased from Aladdin Reagent (Shanghai, China). Silver nitrate (AgNO3), N,N-dimethylacetamide (DMAc) were
The preparation process had been exhibited in Scheme 1, this study focused on preparing Ag-based SERS analysis system for the detection of enrofloxacin hydrochloride (EH) on the PVDF membrane. Briefly, the PVDF membrane was synthesized by the method of non-solvent induced
Scheme 1. (a) The chemical structure of enrofloxacin hydrochloride and (b) the procedure of systhesis and detection. 2
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Fig. 1. The SEM images of PVDF membrane with different amounts of PVP (a: 0 mg, b: 100 mg, c: 300 mg and d: 500 mg) and the corresponding SERS sensitivity with the same amount of Ag NPs.
and assembled on four pieces of membranes with the volume of 1.0, 2.0, 3.0 and 4.0 mL by filtering. The SERS signals changing of EH with the same concentration (10−3 mol L−1) at the peak of 1596 cm−1 were compared (the Raman spectra were presented in the S1). It was significantly observed that the volume of 3.0 mL Ag NPs contributed the maximal SERS intensity. It was obviously observed that the membrane was gradually turning dark with the amount of Ag NPs increasing. Thus, it was easily understood that the coverage of Ag NPs increasing could contribute more significant SERS intensity, but superfluous Ag NPs would be reciprocally stacked and the underneath layer couldn't effectively supply the Raman enhancement signal. Therefore, the optimum amount of Ag NPs was selected as 30 mg (3.0 mL) in this test.
phase separation (NIPS) and fabricated with amount of Ag NPs by suction filtration to prepare the APM. Moreover, in order to enhance the sensitivity and increase the number of “hot spots”, citric acid was selected to regulate morphology of Ag NPs with flower-like. The APM as a kind of flexible materials could more effectively be applied into detection vessels and avoid the waste caused by the centrifugation. This test provided a novel direction of SERS investigation.
3.2. Investigation of optimal conditions In order to get the SERS membrane with high sensitivity, the optical synthesis condition was investigated. Firstly, the amount of PVP was investigated by analyzing the morphologies and SERS properties. As shown in Fig. 1a–d, the morphologies of PVDF membranes were significantly influenced by the amount of PVP and the size and dispersion of pores were gradually uniform with the PVP increasing. Through carefully analyzing to the detection characters, it was found from Fig. S1 that the membrane flux was gradually increasing following with the amount of PVP increasing. However, it also found that when the membranes loaded the same amount of Ag NPs (10 mg), the sensitivity of SERS detection to the same concentration of EH (10−3 mol L−1) was gradually increasing until the amount of PVP was 300 mg and slightly decreasing when the amount of PVP was more than 300 mg. It was speculated that the PVP as the pore-foaming agent could effectively increase the pore size and the membrane flux, but plenty of Ag NPs would get into the inside of the membrane when the pore size was too large. Therefore, the optimum amount of PVP was considered as 300 mg. Secondly, it was considered that the amount of Ag NPs could affect the SERS sensitivity, so the optimal volume of Ag NPs was also investigated through four tests with different volumes of Ag NPs. As shown in Fig. 2a–d, 100 mg Ag NPs were dispersed into 10 mL water
3.3. Characterization of APM The morphologies of the materials synthesized in every step were characterized by SEM. Firstly, as shown in Fig. 3a, the Ag NPs presented flower-like structure and uniform dispersity. Secondly, the morphology of APM modified with 300 mg PVP and 30 mg Ag NPs was investigated. As shown in Fig. 3b, the Ag NPs were dispersed the surface of membrane and presented a little agglomerate. The amount and dispersitity of Ag NPs insured the effective quantity of “hot spots”, which presented high detection sensitivity. Moreover, the filtration of Ag NPs didn't affect the structure of the membrane, which effectively ensured the process of SERS detection. In order to further confirm the preparation of APM, the X-ray diffraction (XRD) investigation was presented. It could be observed from Fig. 4 that the APM appeared four additional peaks comparing to the blank membrane comparing to the blank membrane. The diffraction peaks indexed to the (111), (200), (220) and (311) crystal planes were corresponding to the typical face-centered cubic Ag crystal phase (Li et al., 2017c). It was proved that the Ag NPs had been successfully
Fig. 2. The photographs of APM with different amounts of Ag NPs (a: 1.0 mL, b: 2.0 mL, c: 3.0 mL and d: 4.0 mL) and the corresponding SERS sensitivity. 3
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Fig. 3. The SEM images of (a) flower-like Ag NPs and (b) APM.
membrane, which ensured the solution of EH could smoothly get through the APM (Lu et al., 2018). However, with time of flux increasing, there would be few of EH on the membrane and decreased the membrane flux. The results convincingly proved that the APM could be more effectively applied into processing of EH, which insured the process of SERS detection smoothly proceeding. In order to further confirm the conjecture, the water contact angle was also investigated and the results were presented in Fig. 6a–e. It could be found that the water contact angle was gradually decreased following with the amount of Ag NPs increasing. The excellent water contact angle could ensure the EH adequately contacting with Ag NPs and presented significant SERS signal. Meanwhile, the well hydrophilia could effectively prevent membrane fouling, which could maintain the propitious application of APM. Though the water contact angle of the 30 mg and 40 mg were similar, the SERS sensitivity of 30 mg was the highest. Therefore, the optimal amount of Ag NPs was considered as 30 mg. Fig. 4. The X-ray diffraction patterns of (a) PVDF membrane and (b) APM.
3.4. The detection sensitivity of APM
covered on the surface of PVDF membrane. The property of membrane flux was also an important index to the APM in the process of SERS detection and it was mainly investigated by flux equipment under a pressure of 0.1 Mpa. Briefly, the membrane flux of APM was investigated by filtrating 10 μmol L−1 EH and the blank PVDF membrane was also investigated as the comparison with the same test process. As shown in Fig. 5, the membrane flux of APM was significantly higher than that of blank membrane. Meanwhile, the flux direction of APM was slowly-quickly-steadily and the flux direction of blank membrane was quickly-steadily. It was speculated that the addition of Ag NPs could effectively improve the hydrophilia of the
The sensitivity was also an important index in the detection of EH. Briefly, 10 pieces of APM with the same size about 1.0✕1.0 cm2 were placed on a glass slide and dropwise added EH solution with different concentrations on the APM, respectively. Then the APM was immediately carried to detect by Raman spectrometer. The results were presented in Fig. 7a and it could be found that the SERS intensities gradually weakened with the concentration of EH decreasing. It could be concluded that the APM was sensitive to the concentration changing of EH. Moreover, as shown in Fig. 7b, when the concentration of EH changed between 1.0 nmol L−1 and 200 nmol L−1, there was a linear relationship between SERS intensity and concentration of EH. The coefficient of determination (R2) was 0.9992 and the detection of limit was 0.01 nmol L−1. Therefore, it could be confirmed that the APM could be applied into the EH detection in the aqueous. 3.5. The recycle detection of APM The recycle application was also an important index to the APM in the detection of EH for the superior cyclic performance could decrease the cost of the detection. It was expectative that the SERS substrates could remain the detection sensitivity after rinsing the analytes. As shown in Fig. 8, the recycle application was investigated by 10 consecutive SERS detections and the SERS sensitivity of APM only decreased 9.6% after 10 cycles. The results confirmed that the APM could be applied into recycle detection. 3.6. Comparison between present method and recent literature Many excellent works about antibiotic detection had been reported and some of them were presented to compare with the work in this test. The information of these methods was listed in Table 1. The reported
Fig. 5. The membrane flux of APM with filtration time of 60 min (insert: the membrane flux of blank PVDF membrane filtrating the same time). 4
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Fig. 6. The water contact angle of APM with different amount of Ag NPs (a: 0 mg; b: 10 mg; c: 20 mg; d: 30 mg; e: 40 mg).
methodologies respectively had the superior detection property, such as: detection time and detection of limit. Comparing with these reported literatures, a rapid detection method based on SERS technique was presented in this work. It was carried out a method which ensured detection sensitivity and observably reduced the detection time. Additionally, as the existence of membrane, the APM could be easily recycled and significantly saving the cost. 3.7. The detection mechanism On present, the SERS detection mechanism mainly divided into two modes: electromagnetic enhancement and charge transfer enhancement. Importantly, the enhancement of noble metal particles was mainly caused by electromagnetic enhancement and the surface of noble metal particles would generate surface plasma resonance under laser irradiating, which could significantly enhance the Raman signal of the molecules absorbed on the substrates. Furthermore, the electromagnetic enhancement at the position of “hot spots” was the most significant and the “hot spots” mainly existed at the gaps of double particles or rough surface of SERS substrates. In this test, Ag NPs were used as the SERS substrates and the SERS signal was mainly generated by electromagnetic enhancement. Under the Raman laser irradiating, the surface plasma of Ag NPs would be resonance and the Raman signal of EH molecules would be magnified.
Fig. 8. The recycle detection capacity of APM to the EH under the concentration of 200 nmol L−1.
that the APM presented good recycle property and could be reused at least 10 times. The investigation presented a novel approach to the EH detection on the sensitivity and reducing duration time. The results confirmed that the APM synthesized in this test could be applied into the EH and this method also could be applied into the other antibiotics detection.
4. Conclusion Acknowledgements
In summary, a rapid detection method based on SERS technique was presented. PVDF membrane was selected as the support material and dispersed amount of Ag NPs on the surface to apply into the detection of EH in the water. It was reflected from the investigation results that when the amount of PVP was 300 mg and Ag NPs was 30 mg, the SERS property of APM was the most sensitive. Moreover, the SERS intensity and concentration of EH presented a linear relationship when the concentration of EH changed between 1.0 nmol L−1 and 200 nmol L−1. Through calculating, the coefficient of determination (R2) was 0.9992 and the detection of limit was 0.01 nmol L−1. The recycle test proved
This work is supported by the National Natural Science Foundation (No. 21576112), Natural Science Foundation Project of Jilin Province (,20180623042TC 20180101181JC, 20170520147JH). The Project of Department of Science & Technology of Jilin Province (20180623042 TC, 20170520134JH), the Project of Education Department of Jilin Province (JJKH20191010KJ) and the Project of Human Resources and Social Security Department of Jilin Province (2017956).
Fig. 7. (a) The SERS spectra of EH with different concentrations detected on the APM and (b) the relationship between Raman intensity and concentration of EH as the functional bands at 1596 cm−1. 5
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Table 1 The comparison between present method and recent literature. Antibiotics Chloramphenicol Apramycin Kanamycin Ampicillin Tetracycline Enrofloxacin Hydrochloride
Methodology
Detection Time
Fluorescence HPLC-ELSD Electrochemistry Electrochemical surface plasmon resonance Fluorescence SERS
40 min 10 min 60 min 60 min 30 min Immediately
Appendix A. Supplementary data
Detection of Limit −13
mol/L) 0.033 pg/mL (10 0.2 mg/g (10−7 mol/L) −11 74.50 pmol/L (10 mol/L) 1.0 μmol L−1 50 nmol L−1 10−11 mol/L
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Journal of Environmental Management journal homepage: www.elsevier.com/locate/jenvman
Research article
Rapid and sensitive detection of enrofloxacin hydrochloride based on surface enhanced Raman scattering-active flexible membrane assemblies of Ag nanoparticles
T
⁎
Hongji Lia,b,c, , Mingchao Wangd, Xiaoxue Shenb, Sui Liub, Yan Wange, Yue Lie, ⁎⁎ Qingwei Wanga,c, , Guangbo Chea,c a
Key Laboratory of Preparation and Applications of Environmental Friendly Materials (Jilin Normal University), Ministry of Education, Changchun, 130103, PR China College of Environmental Science and Engineering, Jilin Normal University, Siping, 136000, PR China Key Laboratory of Functional Materials Physics and Chemistry of the Ministry of Education, Jilin Normal University, Changchun 130103, PR China d College of Physics, Jilin Normal University, Siping, 136000, PR China e College of Chemistry, Jilin Normal University, Siping, 136000, PR China b c
A R T I C LE I N FO
A B S T R A C T
Keywords: Surface enhanced Raman scattering Membrane separation Trace analysis Enrofloxacin hydrochloride
The abuse of antibiotics resulted in the pollution of river is more and more serious and it was necessary to exploit a sensitive detection method to improve the traditional analysis measurement. In this test, it is reported an Agbased SERS sensing membrane synthesized by the technique of SERS detection and membrane separation. SERS analysis technique presented sensitive detection property, which could be applied into trace analysis. Membrane separation could effectively enrich the analytes to improve the sensitivity. The SERS membrane was synthesized by filtrating Ag nanoparticles (NPs) on the surface and investigating the amount of PVP and Ag NPs to the sensitivity. Meanwhile, the addition of Ag NPs effectively improved the hydrophilia to promote the detection effectivity in the water. By the investigations of optical analysis, the SERS membrane presented high sensitivity in the detection of antibiotics. Under the optimal condition, the SERS intensity presented good linear relationship with the concentration of antibiotics between 1.0 nmol L−1 and 200 nmol L−1. This method provided a sensitive detection approach and broadened the investigation field of antibiotics detection.
1. Introduction Antibiotics have been widely applied in human and veterinary medicine depending on the excellent ability of bacteriostasis (Tao et al., 2019; Xie et al., 2017). However, residual antibiotics have been detected in most mammals’ excrement and superfluous antibiotics will affect the normal physiological function of human and other mammals (Kim et al., 2015). Therefore, the detection of antibiotics can make a contribution to the environment protection. Up to now, there are lots of analytical methods have been used into antibiotics detection, such as HPLC, GC-MS, TLC and ELISA (Yu et al., 2019a; Ershadi et al., 20017; Tang et al., 2017; Liu et al., 2016; Ha et al., 2014; Huang et al., 2013). However, the traditional methods contain some areas that need improvement, such as: a) the testing process is expensive; b) the process of sample pretreatment is complex; c) the consumption of testing sample is
numerous. Therefore, it is imminently to develop a novel method which could more effectively detect the residual antibiotics. In order to realize the ultratrace sample detection, the surface enhanced Raman scattering (SERS) technology is gradually attracting to the view of scientists. Nowadays, as an ultrasensitive detection method, SERS has been applied into most compounds analysis, such as: organic pollutants, metal ions, endocrine disrupter et al. (Li et al., 2017a, 2018a; Zhou et al., 2017; Fang et al., 2013). Comparing to the traditional analysis approach, SERS technique possesses the merits such as: less analysis dosage, short test time and good repeatability. Though the SERS is a sensitive detection technology, the synthesis of substrates is very rigorous. In order to get more sensitive SERS property, the substrates should possess several targets, such as: a) rough surface morphology; b) regular structures; c) easy to repeat (Li et al., 2017b; Chaunchaiyakul et al., 2017; Huy et al., 2017; Wang et al., 2017). Based
⁎ Corresponding author. Key Laboratory of Preparation and Applications of Environmental Friendly Materials (Jilin Normal University), Ministry of Education, Changchun, 130103, PR China. ⁎⁎ Corresponding author. Key Laboratory of Functional Materials Physics and Chemistry of the Ministry of Education, Jilin Normal University, Changchun 130103, PR China. E-mail addresses: [email protected] (H. Li), [email protected] (Q. Wang).
https://doi.org/10.1016/j.jenvman.2019.109387 Received 22 April 2019; Received in revised form 23 July 2019; Accepted 10 August 2019 0301-4797/ © 2019 Elsevier Ltd. All rights reserved.
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on the considerations, the Ag-based substrates become the first choice of SERS substrate preparation for the characteristics of significant enhancement property, easy preparation and excellent reproducibility (Tao et al., 2016; Gao et al., 2017). Furthermore, it has been widely accept that the SERS signal of the template molecules can be enhanced 6–8 orders when they are adsorbed in the gaps named “hot spots” of Ag NPs (Nie and Emory, 1997; Xinne et al., 2015). Importantly, the greater advantage of SERS detection is that this method doesn't affect by the state of the samples. It can be directly detected and doesn't affect by the residual solvent. However, the SERS substrates of the past are mainly focused on the powders synthesis, which neglects the disadvantage of difficult to recycle. Therefore, it is necessary that develop a synthesis technology to guarantee the effect of sensitive detection and recycle, simultaneously. In recent years, the technology of membrane separation has attracted more and more attention for the superior properties, such as: large surface to volume ratio, excellent flexibility, easy installation, and low cost (Saidi, 2017; Ahmad and Ramli, 2013; Stoquart et al., 2012). Among varies membranes, poly(vinylidene fluoride) (PVDF) presents promising properties due to its peculiar antioxidation activity, excellent chemical resistance, thermal stability, and good membrane-forming properties (Wang et al., 2012; Chiang et al., 2009; Lee et al., 2013). Based on these encouraging properties, it is considered that introduce the technology of membrane separation into the SERS detection to improve the deficiencies. The PVDF membrane exhibits lots of excellent properties, but this material own a serious disadvantage in the antibiotics detection which is hydrophobic nature. Thanks to the nature of hydrophilia and fouling resistance, the modification of Ag NPs not only can supply the property of SERS detection but also can improve the hydrophilia and fouling resistance properties of PVDF membrane, which can effectively increase the cycle times. Herein, it is reported that an Ag-based SERS membrane analysis system for the detection of enrofloxacin hydrochloride (EH) in water. In this investigation, the flower-like Ag NPs are firstly synthesized to make the SERS substrates get more “hot spots”. Then the Ag NPs are fabricated on the PVDF membrane by filtration to prepare the Ag-based PVDF membrane (APM) and the optimal dosage of Ag colloid was also studied to ensure getting the most sensitive APM. This mehod presented a novel analysis measurement which combined SERS technique and membrane separation. It could effectively increase the attachment area and promote the detection sensitivity. Meanwhile, the addition of Ag NPs improved the hydrophilia, which promoted the recycle detection times of APM. Moreover, the morphology, performance and sensitivity were also investigated and it was proved from the results that this APM could be applied into the EH detection in the water.
purchased from Sinopharm Chemical Reagent Co.,Ltd. (Shanghai, China). Doubly distilled water was used in all cleaning processes and aqueous solutions. 2.2. Apparatus and measurements Surface morphology of the samples was analyzed with a scanning electron microscope (SEM, JSM-7800F, JEOL, Japan). Infrared spectra (4000-400 cm−1) were collected on a FT-IR apparatus (Frontier, PE, U.S.A.). X-ray diffraction (XRD) spectra were collected on a X-ray diffractometer (PC2500, RIGAKU, Japan) with Cu Ka radiation over the 2θ range of 30-80°. Raman spectra were obtained by a confocal microRaman spectroscopy system (SENTERRA II, Bruker, Germany). 2.3. Synthesis of flower-like Ag NPs The flower-like Ag NPs were synthesized as follows: 170 mg AgNO3 solution and 1.92 g citric acid were dispersed into 60 mL distilled water. Then 500 mg ascorbic acid was added into the mixture system under stirring. After 1.0 h, the black precipitate was gathered by centrifugation and dried in vacuum. 2.4. Fabrication of APM Firstly, the PVDF membrane was synthesized by the method of nonsolvent induced phase separation (NIPS): 4.0 g PVDF powder was dispersed into 20 mL DMAc and the system was stirred under room temperature. Subsequently, a certain amount of PVP powder was added and continued stirring 24 h. Then the solution was placed 12 h for exhausting the mixture gas and casted the PVDF membrane on a clean glass plate. The glass plate was immersed into water and accomplished the procedure of phase inversion to obtain the PVDF membrane. Secondly, the flower-like Ag NPs were assembled on the surface of PVDF membrane by suction filtration: a certain amount of Ag dispersion liquid was dropped on the surface of PVDF membrane and the solution was carried out suction filtration under the pressure of 0.1 Mpa. 2.5. Raman detection measurement The SERS detection capability of APM was reflected by Raman detection. In this experiment, all the Raman detections were under the uniform conditions: the excitation was 532 nm. The spectra of each sample were collected with an exposure time of 10 s and incident laser power of 0.25 mW. SERS spectra were collected using a 50 × Nikon objective.
2. Experiment section 3. Results and discussion 2.1. Chemicals and materials 3.1. Procedure of APM synthesis Enrofloxacin hydrochloride (EH) was purchased from National Institutes for Food and Drug Control. PVDF powder was purchased from French company Arkema. Polyvinylpyrrolidone (PVP, k30), citric acid, ascorbic acid were purchased from Aladdin Reagent (Shanghai, China). Silver nitrate (AgNO3), N,N-dimethylacetamide (DMAc) were
The preparation process had been exhibited in Scheme 1, this study focused on preparing Ag-based SERS analysis system for the detection of enrofloxacin hydrochloride (EH) on the PVDF membrane. Briefly, the PVDF membrane was synthesized by the method of non-solvent induced
Scheme 1. (a) The chemical structure of enrofloxacin hydrochloride and (b) the procedure of systhesis and detection. 2
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Fig. 1. The SEM images of PVDF membrane with different amounts of PVP (a: 0 mg, b: 100 mg, c: 300 mg and d: 500 mg) and the corresponding SERS sensitivity with the same amount of Ag NPs.
and assembled on four pieces of membranes with the volume of 1.0, 2.0, 3.0 and 4.0 mL by filtering. The SERS signals changing of EH with the same concentration (10−3 mol L−1) at the peak of 1596 cm−1 were compared (the Raman spectra were presented in the S1). It was significantly observed that the volume of 3.0 mL Ag NPs contributed the maximal SERS intensity. It was obviously observed that the membrane was gradually turning dark with the amount of Ag NPs increasing. Thus, it was easily understood that the coverage of Ag NPs increasing could contribute more significant SERS intensity, but superfluous Ag NPs would be reciprocally stacked and the underneath layer couldn't effectively supply the Raman enhancement signal. Therefore, the optimum amount of Ag NPs was selected as 30 mg (3.0 mL) in this test.
phase separation (NIPS) and fabricated with amount of Ag NPs by suction filtration to prepare the APM. Moreover, in order to enhance the sensitivity and increase the number of “hot spots”, citric acid was selected to regulate morphology of Ag NPs with flower-like. The APM as a kind of flexible materials could more effectively be applied into detection vessels and avoid the waste caused by the centrifugation. This test provided a novel direction of SERS investigation.
3.2. Investigation of optimal conditions In order to get the SERS membrane with high sensitivity, the optical synthesis condition was investigated. Firstly, the amount of PVP was investigated by analyzing the morphologies and SERS properties. As shown in Fig. 1a–d, the morphologies of PVDF membranes were significantly influenced by the amount of PVP and the size and dispersion of pores were gradually uniform with the PVP increasing. Through carefully analyzing to the detection characters, it was found from Fig. S1 that the membrane flux was gradually increasing following with the amount of PVP increasing. However, it also found that when the membranes loaded the same amount of Ag NPs (10 mg), the sensitivity of SERS detection to the same concentration of EH (10−3 mol L−1) was gradually increasing until the amount of PVP was 300 mg and slightly decreasing when the amount of PVP was more than 300 mg. It was speculated that the PVP as the pore-foaming agent could effectively increase the pore size and the membrane flux, but plenty of Ag NPs would get into the inside of the membrane when the pore size was too large. Therefore, the optimum amount of PVP was considered as 300 mg. Secondly, it was considered that the amount of Ag NPs could affect the SERS sensitivity, so the optimal volume of Ag NPs was also investigated through four tests with different volumes of Ag NPs. As shown in Fig. 2a–d, 100 mg Ag NPs were dispersed into 10 mL water
3.3. Characterization of APM The morphologies of the materials synthesized in every step were characterized by SEM. Firstly, as shown in Fig. 3a, the Ag NPs presented flower-like structure and uniform dispersity. Secondly, the morphology of APM modified with 300 mg PVP and 30 mg Ag NPs was investigated. As shown in Fig. 3b, the Ag NPs were dispersed the surface of membrane and presented a little agglomerate. The amount and dispersitity of Ag NPs insured the effective quantity of “hot spots”, which presented high detection sensitivity. Moreover, the filtration of Ag NPs didn't affect the structure of the membrane, which effectively ensured the process of SERS detection. In order to further confirm the preparation of APM, the X-ray diffraction (XRD) investigation was presented. It could be observed from Fig. 4 that the APM appeared four additional peaks comparing to the blank membrane comparing to the blank membrane. The diffraction peaks indexed to the (111), (200), (220) and (311) crystal planes were corresponding to the typical face-centered cubic Ag crystal phase (Li et al., 2017c). It was proved that the Ag NPs had been successfully
Fig. 2. The photographs of APM with different amounts of Ag NPs (a: 1.0 mL, b: 2.0 mL, c: 3.0 mL and d: 4.0 mL) and the corresponding SERS sensitivity. 3
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Fig. 3. The SEM images of (a) flower-like Ag NPs and (b) APM.
membrane, which ensured the solution of EH could smoothly get through the APM (Lu et al., 2018). However, with time of flux increasing, there would be few of EH on the membrane and decreased the membrane flux. The results convincingly proved that the APM could be more effectively applied into processing of EH, which insured the process of SERS detection smoothly proceeding. In order to further confirm the conjecture, the water contact angle was also investigated and the results were presented in Fig. 6a–e. It could be found that the water contact angle was gradually decreased following with the amount of Ag NPs increasing. The excellent water contact angle could ensure the EH adequately contacting with Ag NPs and presented significant SERS signal. Meanwhile, the well hydrophilia could effectively prevent membrane fouling, which could maintain the propitious application of APM. Though the water contact angle of the 30 mg and 40 mg were similar, the SERS sensitivity of 30 mg was the highest. Therefore, the optimal amount of Ag NPs was considered as 30 mg. Fig. 4. The X-ray diffraction patterns of (a) PVDF membrane and (b) APM.
3.4. The detection sensitivity of APM
covered on the surface of PVDF membrane. The property of membrane flux was also an important index to the APM in the process of SERS detection and it was mainly investigated by flux equipment under a pressure of 0.1 Mpa. Briefly, the membrane flux of APM was investigated by filtrating 10 μmol L−1 EH and the blank PVDF membrane was also investigated as the comparison with the same test process. As shown in Fig. 5, the membrane flux of APM was significantly higher than that of blank membrane. Meanwhile, the flux direction of APM was slowly-quickly-steadily and the flux direction of blank membrane was quickly-steadily. It was speculated that the addition of Ag NPs could effectively improve the hydrophilia of the
The sensitivity was also an important index in the detection of EH. Briefly, 10 pieces of APM with the same size about 1.0✕1.0 cm2 were placed on a glass slide and dropwise added EH solution with different concentrations on the APM, respectively. Then the APM was immediately carried to detect by Raman spectrometer. The results were presented in Fig. 7a and it could be found that the SERS intensities gradually weakened with the concentration of EH decreasing. It could be concluded that the APM was sensitive to the concentration changing of EH. Moreover, as shown in Fig. 7b, when the concentration of EH changed between 1.0 nmol L−1 and 200 nmol L−1, there was a linear relationship between SERS intensity and concentration of EH. The coefficient of determination (R2) was 0.9992 and the detection of limit was 0.01 nmol L−1. Therefore, it could be confirmed that the APM could be applied into the EH detection in the aqueous. 3.5. The recycle detection of APM The recycle application was also an important index to the APM in the detection of EH for the superior cyclic performance could decrease the cost of the detection. It was expectative that the SERS substrates could remain the detection sensitivity after rinsing the analytes. As shown in Fig. 8, the recycle application was investigated by 10 consecutive SERS detections and the SERS sensitivity of APM only decreased 9.6% after 10 cycles. The results confirmed that the APM could be applied into recycle detection. 3.6. Comparison between present method and recent literature Many excellent works about antibiotic detection had been reported and some of them were presented to compare with the work in this test. The information of these methods was listed in Table 1. The reported
Fig. 5. The membrane flux of APM with filtration time of 60 min (insert: the membrane flux of blank PVDF membrane filtrating the same time). 4
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Fig. 6. The water contact angle of APM with different amount of Ag NPs (a: 0 mg; b: 10 mg; c: 20 mg; d: 30 mg; e: 40 mg).
methodologies respectively had the superior detection property, such as: detection time and detection of limit. Comparing with these reported literatures, a rapid detection method based on SERS technique was presented in this work. It was carried out a method which ensured detection sensitivity and observably reduced the detection time. Additionally, as the existence of membrane, the APM could be easily recycled and significantly saving the cost. 3.7. The detection mechanism On present, the SERS detection mechanism mainly divided into two modes: electromagnetic enhancement and charge transfer enhancement. Importantly, the enhancement of noble metal particles was mainly caused by electromagnetic enhancement and the surface of noble metal particles would generate surface plasma resonance under laser irradiating, which could significantly enhance the Raman signal of the molecules absorbed on the substrates. Furthermore, the electromagnetic enhancement at the position of “hot spots” was the most significant and the “hot spots” mainly existed at the gaps of double particles or rough surface of SERS substrates. In this test, Ag NPs were used as the SERS substrates and the SERS signal was mainly generated by electromagnetic enhancement. Under the Raman laser irradiating, the surface plasma of Ag NPs would be resonance and the Raman signal of EH molecules would be magnified.
Fig. 8. The recycle detection capacity of APM to the EH under the concentration of 200 nmol L−1.
that the APM presented good recycle property and could be reused at least 10 times. The investigation presented a novel approach to the EH detection on the sensitivity and reducing duration time. The results confirmed that the APM synthesized in this test could be applied into the EH and this method also could be applied into the other antibiotics detection.
4. Conclusion Acknowledgements
In summary, a rapid detection method based on SERS technique was presented. PVDF membrane was selected as the support material and dispersed amount of Ag NPs on the surface to apply into the detection of EH in the water. It was reflected from the investigation results that when the amount of PVP was 300 mg and Ag NPs was 30 mg, the SERS property of APM was the most sensitive. Moreover, the SERS intensity and concentration of EH presented a linear relationship when the concentration of EH changed between 1.0 nmol L−1 and 200 nmol L−1. Through calculating, the coefficient of determination (R2) was 0.9992 and the detection of limit was 0.01 nmol L−1. The recycle test proved
This work is supported by the National Natural Science Foundation (No. 21576112), Natural Science Foundation Project of Jilin Province (,20180623042TC 20180101181JC, 20170520147JH). The Project of Department of Science & Technology of Jilin Province (20180623042 TC, 20170520134JH), the Project of Education Department of Jilin Province (JJKH20191010KJ) and the Project of Human Resources and Social Security Department of Jilin Province (2017956).
Fig. 7. (a) The SERS spectra of EH with different concentrations detected on the APM and (b) the relationship between Raman intensity and concentration of EH as the functional bands at 1596 cm−1. 5
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Table 1 The comparison between present method and recent literature. Antibiotics Chloramphenicol Apramycin Kanamycin Ampicillin Tetracycline Enrofloxacin Hydrochloride
Methodology
Detection Time
Fluorescence HPLC-ELSD Electrochemistry Electrochemical surface plasmon resonance Fluorescence SERS
40 min 10 min 60 min 60 min 30 min Immediately
Appendix A. Supplementary data
Detection of Limit −13
mol/L) 0.033 pg/mL (10 0.2 mg/g (10−7 mol/L) −11 74.50 pmol/L (10 mol/L) 1.0 μmol L−1 50 nmol L−1 10−11 mol/L
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