Novel Biomimic Crystalline Colloidal Array for Fast Detection of Trace

Jun 14, 2017 - Residues of pesticides and veterinary drugs in food and environment are a great hidden danger threatening human health. Parathion is a ...
0 downloads 14 Views 2MB Size
Download PDF
Subscriber access provided by CORNELL UNIVERSITY LIBRARY

Article

A Novel biomimic crystalline colloidal array for fast detection of trace parathion Xihao Zhang, Yanguang Cui, Jialei Bai, zhiyong sun, Baoan Ning, Shuang Li, Jiang Wang, Yuan Peng, and Zhixian Gao ACS Sens., Just Accepted Manuscript • DOI: 10.1021/acssensors.7b00281 • Publication Date (Web): 14 Jun 2017 Downloaded from http://pubs.acs.org on June 19, 2017

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

ACS Sensors is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 8

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sensors

A Novel biomimic crystalline colloidal array for fast detection of trace parathion Xihao Zhang,†,#, ID Yanguang Cui,†,# Jialei Bai,† Zhiyong Sun, ‡ Baoan Ning,† Shuang Li,† Jiang Wang,† Yuan Peng,†,* Zhixian Gao†,* †

Tianjin Key Laboratory of Risk Assessment and Control Technology for Environment and Food Safety, Tianjin Institute of Health and Environmental Medicine, Tianjin, 300050, P. R. China ‡

No.11 Hospital of PLA, Yining, 835000, China

ABSTRACT: A novel gold doped inverse opal photonic crystal (IO PC) was successfully fabricated with combination of molecularly imprinted technical for the fast determination of parathion. Firstly, a closest silica array arrangement behaved as the 3D photonic crystal precursors to build the opal photonic crystal (O PC). Secondly, the parathion-containing polymeric solution with gold nanoparticles was drawn into the 3D array cracks. After polymerization, the well-designed O PC was treated with HF solution for the etching of silica skeleton. Finally, the template parathion was removed and the Au-MIP IO PCs were obtained. The morphology of SiO2 and Au NPs were characterized by transmission electron microscopy (TEM) and the eluted influence of the IO PCs were monitoring by the scanning electron microscopy (SEM). The crosslinking effect was well optimized according to the best spectrum signal of parathion. The as-synthesized Au-MIP IO PCs displayed the specificity towards parathion and the selectivity to other competitive pesticide molecules. The responsive time was only 5 minutes and the parathion could be well detected from real water samples and the recoveries were between 95.5% and 101.5%.

KEYWORDS: inverse opal photonic crystal, Au NPs, parathion, fast detection, high specificity

molecules16-19. These sensors showed opal signal responses accompanied with colour change as the ordered PCs were swell or shrunken when immerged in surrounding environment. The recognition elements of PCs sensors were constructed by direct synthesis or post modified. Meanwhile, molecularly imprinted technique (MIT)20-22, possessing the characterization of high selectivity and specificity, could assist PCs to play advantages in opal sensing. And a series of reported work was concerned with molecularly imprinted polymers (MIPs) and PCs23-25.

Residues of pesticides and veterinary drugs in food and environment are great hidden danger threatening human health. Parathion is a kind of broad-spectrum pesticides, which could be harmful to nervous system, reproductive system, endocrine system and immune system1,2 in case of inhalation or ingestion by human body. The prohibition of parathion has been enforced in many countries and organizations and the maximum residue levels (MRLs) have also been admitted as zero tolerance3. At present, the conventional methods of the detection of parathion mainly rely on large-scale instrument such as high performance liquid chromatography (HPLC)4 or high performance liquid chromatography/mass spectrometry (HPLC/MS)5-7. These methods hold high sensitivity and accuracy, while it takes so much time for the complicated pre-treated and operated process that they are not suitable for rapid and local detection. Other detected methods, just as immunoassay8-10, display high selectivity, whereas the high cost of the antibody shows less stability and harsh preserved conditions. Thus, a highly efficient method that could be time-saving, intuitive and applicable for local and fast detection of parathion is necessary. If it is free enzyme labelled, that would be more superior.

Localized surface plasmon resonance (LSPR) phenomenon occurred when the nanoparticles of noble metals26,27, just as silver, gold and platinum, were excited by incident light. At this moment, the intensity of surface electromagnetic field was enhanced for the synergistic oscillations of free electrons. The energy enhancement effect was more significant in the local space. Based on this, the efficiency of many optical processes has been remarkably improved and the typical model was the application of gold nanoparticles in surface enhanced raman spectroscopy (SERS)28,29. In addition, the sensors built by LSPR were widely used in other areas, such as environmental protection30-32, bio-engineering33-35 and food safety36,37. Tang et al38 prepared an innovative gold nanorod (GNR) array biochip for the signal amplification in molecular beacon detection. The spacer thickness of the GNR surface was optimized and the effect of spectral overlap of the gold nanoparticles with the excitation/emission wavelengths was

Photonic crystals (PCs), behaving as a novel kind of sensors, have been attracted more attention11. The responsive PCs could be affected by the changes of physical quantities12,13, concentration of chemical agents14,15 and even the introduction of biological

1 ACS Paragon Plus Environment

ACS Sensors

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 8

Synthesis of SiO2 nanoparticles (SiO2 NPs). The preparation of silica nanoparticles was carried out through the Stӧber method according to the literature40. Ethanol (50mL) and distilled water (10mL) were injected into a 100mL three-necked flask, then ammonium hydroxide (2.0/2.5/3.0mL) and TEOS (3mL) was added, respectively. The reactant was vigorous mechanically stirring for 24h at room temperature. The as-synthesized SiO2 was collected by centrifugation at different rotation rate for 10 min, after which the SiO2 was re-dispersed by ethanol and centrifugation for several times.

obtained. By contrast experiments, fluorescence enhancement by the GNR array could efficiently overcome the quenching effect owing to the LSPR effect. The introduction of gold nanoarray led to the lower detection limit than conventional sensors. Lin and his co-workers39 presented the Au NPs doped colorimetric biosensor for the ultrasensitive detection of H5N1 virus through the immunoassay method. A silver shell coated Au nanobipyramids (Au NBPs) showed blue shift of LSPR band accompanied with vivid color change. The sensor exhibited the lower LOD of H5N1 virus antigen than previous work due to its highly uniform Au NBPs. It was well known that the sensors built on LSPR displayed signal amplification phenomenon with label-free feature, high sensitivity and less pollution. Among our previous work, the PC sensors were constructed by inverse opal structure, while only the intensity decrease of the peak was observed39. Based on the reported work and the advantages of LSPR system, we attempted to optimize the detective effect for parathion with the extra Au NPs to fulfill a rapid and local determination.

Assemble of opal photonic crystals (O PCs). The O PCs were fabricated by vertical convective self-assembly. The precursor suspension of crystalline colloidal array was obtained with 1% (w%, deionized water) SiO2 nanoparticles by sonication for at least 30min. The above dispersions were placed in open glass beakers inside a constant temperature and constant humidity chamber (Ningbo Haishu Saifu experimental apparatus) at 35°C with humidity of 40% for three to four days to ensure that the solvent water was volatile thoroughly.

Herein, a kind of inverse opal photonic crystals (IO PCs) was developed by PCs coupling with MIPs for the determination of parathion. Besides, gold nanoparticles were doped for signal amplification. The IO PCs held a well periodical structure and showed a favorable spectrum signal to parathion after optimum of eluted effect and cross-linking dosage. The Au-MIPs IO PCs took a rapid response to template parathion specifically and selectively owning to the MIT. Finally, the method was applied for the detection of real tap water and river water samples and the satisfactory results were obtained from spiking experiments.

Synthesis of gold nanoparticles (Au NPs) 41. Oleyl amine (5mL) was added into 25mL flask and heated to 150°C with nitrogen protection. HAuCl4•3H2O (0.3mmol) and oleyl amine (1mL) were injected fast into the system. The reaction was kept at 150°C for 1.5h, and the Au NPs were collected by centrifugation at 11000rpm for 15min twice. The above products were dispersed into hexane (2mL) and propanol (2mL) with further addition of 11-MUA (10mg). The obtained Au NPs were collected by centrifugation at 15000rpm for 15min, and then redispered into methanol (2mL) for further use.

MATERIALS AND METHODS

Synthesis of MIPs. The polymeric solution was consisted of template molecule (parathion), monomer (MAA and NIPA), cross-linker (EGDMA), initiator (AIBN) and solvent (methanol with addition of Au NPs). The dosage was listed in detail in Table 1. The polymeric solution was well solved and vibrated slowly overnight. An intelligent sandwich structure chamber was fabricated by fixing with a clip, wherein the upper portion was a glass slide, the middle portion was the opal SiO2 framework and the lower portion was made of poly(methyl methacrylate) (PMAA) Plexiglas. Then, the polymeric solution was used to fill the spaces of the sandwich structure. The polymerization in the sandwich structure was performed in a 60°C water bath for 4h, and then the 3D ordered inverse opal Au-MIP PCs were formed.

Chemicals and apparatus. Tetraethyl orthosilicate (TEOS), oleyl amine, HAuCl4•3H2O, 11-mercaptoundecanoic acid (11-MUA), methacrylic acid (MAA), N-isopropyl acrylamide (NIPA), ethylene glycol dimethacrylate (EGDMA), 2,2’-azodiisobutyronitrile (AIBN) were purchased from J&K Scientific Ltd (Beijing, China). Parathion, methyl parathion, monocrotophos and malathion were supplied from Sigma (St. Louis, MO, USA). Ammonium hydroxide (NH3•H2O), methanol (MeOH), ethanol (EtOH), n-propanol, n-hexane, acetic acid (HAc), hydrofluoric acid (HF, 40%), sulfuric acid (H2SO4, 98%), hydrogen peroxide (H2O2, 30%) were obtained from Tianjin Chemical Reagent Company (Tianjin, China). Deionized water was prepared with a Milli-Q water purification system (Millipore, Milford, MA). All reagents used were of analytical grade and used without further treatment.

Table 1 The Dosage of each component in polymeric solution

Common glass slides were immersed in a H2SO4/H2O2 (7:3, v/v) mixture for 12 h, followed by rinsing with deionized water in an ultrasonic bath three times and then dried prior for further use. The transmission electron microscope (TEM) images were obtained from a Tecnai G2 T2 S-TWIN and scanning electron microscopy (SEM) were from a SS-550. The reflection spectra were recorded with an Ocean Optics Maya 2000 PRO fiber optic spectrometer (Ocean Optics, Dunedin, FL, USA). The constant temperature and humidity chamber was purchased from Ningbo HaishuSaifu Experimental Instrument Co., Ltd.

Parathion

MAA

NIPA

AIBN

EGDMA

Au NPs

(mL)

(mL)

(mg)

(mg)

(mL)

(MeOH, mL)

1

0.023

0.34

168

10

0.05

0.66

2

0.023

0.34

168

10

0.10

0.66

3

0.023

0.34

168

10

0.15

0.66

4

0.023

0.34

168

10

0.20

0.66

Preparation of gold NPs doped MIPs IO PCs

2 ACS Paragon Plus Environment

Page 3 of 8

Formation of Au-MIPs IO PCs. The 3D ordered Au-MIP was dipped into 1% HF (aq) for 12h to remove the opal SiO2 framework. The target molecules were removed using a mixture of methanol and glacial acetic acid (18:1, v/v) at 10min for several times. Finally, residual organic solvent was removed by deionized water, and the Au-MIP IO PCs were obtained.

Polymerzation

By contrast, three kinds of other PCs were synthesized. The non-imprinted photonic crystals doped with Au NPs (Au-NIPs IO PCs) were prepared in the same way, without addition of target molecules. Besides, molecularly imprinted photonic crystals (MIPs IO PCs) were prepared in the same way, without addition of Au NPs. Finally, non-imprinted photonic crystals (NIPs IO PCs) were prepared with neither target molecules nor Au NPs.

HF etching

template removing

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sensors

rebinding

Spectroscopic characterizations of the specificity and selectivity of Au-MIPs IO PCs towards parathion. The Au-MIP IO PCs were placed into deionized water for at least 8h to keep stable. The fiber probe of the spectrometer was fixed vertically above the PCs surface at room temperature (25°C). The concentrations of the template molecule (parathion) were gradually increased from 1×10-3 ng mL-1 to 1 µg mL-1, and the responses were recorded. All experiments were carried out in the same conditions for the other three PCs.

SiO 2

parathion

Au NPs

Scheme 1 Synthetic procedure of Au MIPs IO PCs. Preparation and characterization Au-MIPs IO PCs. Typical TEM images of SiO2 NPs and Au NPs were shown in Fig. 1. The diameter of Au NPs was about ~15nm after ligand substitution and solvent transfer. The diameter of SiO2 NPs was controlled by the amount of NH3•H2O. It could be observed that the particle size increased by the successive addition of NH3•H2O with an average diameter of ~200nm, 300nm and 400nm.

Methyl parathion, monocrotophos and malathion were selected as structural analogues. Selective experiments were carried out in the same procedure with concentrations from 1×10-3 ng mL-1 to 1 µg mL-1 of all the three analytes by the Au-MIP IO PCs and MIPs IO PCs. Real samples analysis. Tap water and river water (Haihe River, Tianjin, China) were collected as real sample analysis. The two samples were only filtered before use. The spiking concentrations of parathion were 0.01 ng mL-1 and 0.1µg mL-1. The detective procedure was the same as the standard parathion solutions.

RESULTS AND DISCUSSION The protocol for the synthesis of Au-MIP IO PCs is illustrated in Scheme 1. SiO2 nanoparticles, prepared by Stӧber method, were utilized for opal crystalline colloidal array. A pre-polymeric solution containing template parathion was injected into the gap of crystalline colloidal array and molecularly imprinted polymers were formed by thermal initiation. After SiO2 were etched by HF, the IO PCs were obtained, while the net-structural polymer could be stable with the addition of cross-linker EGDMA. Finally, the template was removed by organic solvent. Figure 1. TEM images of Au NPs (a) and SiO2 NPs: ~200nm(b), ~300nm(c), ~400nm(d). The crystalline colloidal array was stacked by the above three different SiO2 NPs. Nevertheless, only the ones with ~300nm diameter could be well stacked after lying in the constant temperature and constant humidity chamber for 3-4 days. The SEM images were shown in Fig. 2(a). The crystalline colloidal array held the (111) plane of the face centered cubic (FCC) lattice structure.

3 ACS Paragon Plus Environment

ACS Sensors

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 4 of 8

Figure 2. SEM images of O PCs(a) and IO PCs(b). The eluted level of template would have an important influence in the rebinding effect of Au-MIP IO PCs. Admittedly, the thorough removal of template could benefit the binding capacity; nevertheless, the introduced organic solvent would destroy the net-structure of Au-MIP IO PCs so that the IO PCs could not keep self-structure. Thus, the eluted times have been optimized. The eluted concentration of parathion was measured by UV-Vis spectroscopy at 271nm with methanol and acetic acid (18:1, v/v) as solvent. The elution time lasted for 2h, equally 12 times (10min each time). The residue concentration was listed in Fig.S1 and the SEM images exhibited the morphology after 6 times, 9 times and 12 times in Fig. S2-S5 (See Supporting Informations). Partial structure was destroyed slightly after 6 times, and the periodical array was kept relatively intact. The destructed area enlarged and partial net-structure was collapsed after 9 times. What’s worse, the periodical array could not be kept complete to some extent. When eluted by 12 times, it was pity that a major ruin of the periodical array could be seen by naked eyes and the polymer seemed very fragile intuitively. At this point, the hybrid composited could not be named as photonic crystals since it did not possess the corresponding optical character. The rigid construction could be kept by the introduction of cross-linker EGDMA. While the different addition of EGDMA(0.5/1.0/1.5/2.0 mL) exhibited the same tendency in Fig. S2-S5, excess amount of EGDMA could not preserve the rigid construction still.

Figure 3. Response time of Au MIPs IO PCs in parathion solution (1µg mL-1). Template rebinding experiments were carried out by a successive addition of parathion and the signal changes were monitored by the fiber probe of the spectrometer. Methanol played as synthetic and detective solvent according to previous work42. Fig. 4 showed the influence of cross-linker EGDMA. Generally speaking, only the decrease of diffraction peak could be observed with the sensors built by the inverse opal photonic crystals. However, the doped Au NPs provided an additional red shift of wavelength. In all of the results from fig. 4a-4d, the red shift phenomenon existed more or less, particularly in 4b when EGDMA was 0.1mL. Besides, the decrease of diffraction peak presented a similar tendency. The summarized results were listed in Table 2. The reason might lie in two aspects: (a) the binding capacity of Au-MIP IO PCs towards parathion was increased with the added content of EGDMA in polymeric solution initially, (b) whereas the structure of polymer became too rigid to combine more parathion with a further addition of EGDMA. Thus, the additive content of 0.1mL was suitable for detection of target molecule and subsequent experiments.

Fortunately, the parathion residue significantly reduced after 6 times. A consecutive elution hardly played an important role for removal of template. Considering both of the factors above, 6 times was chosen as the optimal eluted time for further experiments. The SEM images after 6 times elution of Au-MIP IO PCs were shown in fig. 2(b) and fig. S2(a)-S5(a). Binding properties of Au-MIPs IO PCs. The responsive time was investigated by incubating the Au-MIP IO PCs into parathion solution (1µg mL-1) for 1-10min. As shown in Fig. 3, the quick adsorptive equilibrium was obtained within only 5min. It was attributed to the fast mass transfer of the surface molecularly imprinted technique and the template molecule could diffuse into the IO PCs for its large surface area.

Figure 4. Optical responses of Au MIPs IO PCs towards parathion with different content of EGDMA: (a) 0.05mL, (b) 0.1mL, (c) 0.15mL and (d) 0.2mL.

4 ACS Paragon Plus Environment

Page 5 of 8

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sensors

Table 2 Data summary of optical responses of Au MIPs IO PCs towards parathion with different content of EGDMA EGDMA(mL)

Red shift (nm)

concluded that not only the imprinted cavities played an important role in recognition with template molecules, but also the doped Au NPs had contributions to the red shift effect. It was noteworthy that the Au NPs did not work when there were no imprinted cavities left, only the effective responsive signal could be enlarged by doped Au NPs.

Peak decrease(a.u.)

1

0.05

7

9

2

0.10

14

15

3

0.15

7

5

4

0.20

3

2

Molecularly imprinted effect was tested with the detection of parathion by Au-NIP IO PCs. Au-NIP IO PCs were prepared in the absence of the template parathion, suggesting that there were no imprinted cavities for fixing with parathion. From fig. 5b, as the concentration of analyte increased gradually, there was no obvious change of peak intensity, not to mention a red shift of diffraction wavelength comparing to the imprinted effect by the Au-MIP IO PCs(here the figure 5a was the same as figure 4b).

Figure 7. Data summary of red shift of four kinds of IO PCs towards parathion. Selectivity experiments were studied by Au-MIP IO PCs and MIP IO PCs. Three kinds of pesticides, methyl parathion, monocrotophos and malathion were selected as structural analogues. The adsorption data were shown in Fig. 8. At a glance, there was no change of peak intensity or diffraction wavelength. In other words, the synthetic Au-MIP IO PCs and MIP IO PCs showed no response to these three pesticides, which meant that the Au-MIP IO PCs and MIP IO PCs presented favorable selectivity to template molecule. Meanwhile, the selectivity of MIP IO PCs was not influenced by doped Au NPs.

Figure 5. Optical responses of Au MIPs IO PCs(a) and Au NIP IO PCs(b) towards parathion. Beyond above, the function of the doped Au NPs was investigated. Both MIP IO PCs and NIP IO PCs were fabricated without doped Au NPs. The combination behaviors of MIP IO PCs and NIP IO PCs towards parathion were present in fig. 6a and 6b. For MIP IO PCs (6a), there was hardly red shift of diffraction wavelength, and it was merely showed a decrease of peak intensity. Moreover, the degree of decline was not a patch on that of Au-MIP IO PCs. When the parathion concentration was up to 0.01µg mL-1 or even more, the peak intensity did not fall down any more, while the Au-MIP IO PCs could offer a continuous decrease until 1µg mL-1 of parathion. The NIP IO PCs with neither imprinted cavities nor doped Au NPs behaved so poor as our expected (6b). There was not any response with the increase of the parathion concentration.

Figure 8. Optical responses of Au-MIP IO PCs towards methyl parathion(a), monocrotophos(c), malathion(e) and MIP IO PCs towards methyl parathion(b), monocrotophos(d), malathion(f). Real sample analysis. Two kinds of water from different resources, tap water and river water were spiked with parathion. The results were listed in table 3. The spiking recoveries were from 95.5% to 101.5% and the RSD (n=5) was below 5%, which

Figure 6. Optical responses of MIPs IO PCs(a), NIPs IO PCs(b) towards parathion. The data collection given by fig. 7 exhibited the red shift effect of the four synthetic hybrid composites directly. It could be

5 ACS Paragon Plus Environment

ACS Sensors

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Reduces Organophosphate Pesticide Absorption and Toxicity to Drosophila melanogaster. Appl. Environ. Microb. 2016, 82(20), 6204-6213. (2) Liu, J.; Parsons, L.; Pope, C. Comparative effects of parathion and chlorpyrifos on endocannabinoid and endocannabinoid-like lipid metabolites in rat striatum. Neurotoxicology 2015, 50, 20-27. (3) Liu, Y.H.; Shen, D.Y.; Li, S.L.; Ni, Z.L.; Ding, M.; Ye, C.F.; Tang, F.B. Residue levels and risk assessment of pesticides in nuts of China. Chemosphere 2016, 144, 645-651. (4) Chen, J.H; Zhou, G.M.; Deng, Y.L.; Cheng, H.M.; Shen, J.; Gao, Y.; Peng, G.L. Ultrapreconcentration and determination of organophosphorus pesticides in water by solid-phase extraction combined with dispersive liquid-liquid microextraction and high-performance liquid chromatography. J. Sep. Sci. 2016, 39(2), 272-278. (5) Zare, M.; Ramezani, Z.; Rahbar, N. Development of zirconia nanoparticles-decorated calcium alginate hydrogel fibers for extraction of organophosphorous pesticides from water and juice samples: Facile synthesis and application with elimination of matrix effects. J. Chromatogr. A 2016, 1473, 28-37. (6) Grandy, J.J.; Boyaci, E.; Pawliszyn, J. Development of a Carbon Mesh Supported Thin Film Microextraction Membrane As a Means to Lower the Detection Limits of Benchtop and Portable GC/MS Instrumentation. Anal. Chem. 2016, 88(3), 1760-1767. (7) Zheng, L.L.; Pi, F.W.; Wang, Y.F.; Xu, H.; Zhang, Y.Z.; Sun, X.L. Photocatalytic degradation of Acephate, Omethoate, and Methyl parathion by Fe3O4@SiO2@mTiO(2) nanomicrospheres. J. Hazard Mater. 2016, 315, 11-22. (8) Mehta, J.; Vinayak, P.; Tuteja, S.K.; Chhabra, V.A.; Bhardwaj, N.; Paul, A.K.; Kim, K.H.; Deep, A. Graphene modified screen printed immunosensor for highly sensitive detection of parathion. Biosens. Bioelectron. 2016, 83, 339-346. (9) Wang, H.M.; Zhao, F.C.; Han, X.; Yang, Z.Y. Production and characterization of a biotinylated single-chain variable fragment antibody for detection of parathion-methyl. Protein Expres. Purif. 2016, 126, 1-8. (10) Shu, Q.; Wang, L.M.; Ouyang, H.; Wang, W.W.; Liu, F.Q.; Fu, Z.F. Multiplexed immunochromatographic test strip for time-resolved chemiluminescent detection of pesticide residues using a bifunctional antibody. Biosens. Bioelectron. 2017, 87, 908-914. (11) Fenzl, C.; Hirsch, T.; Wolfbeis, O.S. Photonic Crystals for Chemical Sensing and Biosensing. Angew. Chem. Int. Ed. 2014, 53, 3318 – 3335. (12) Fsaifes, I.; Feugnet, G.; Ravaille, A.; Debord, B.; Gerome, F.; Baz, A.; Humbert, G.; Benabid, F.; Schwartz, S.; Bretenaker, F. A test resonator for Kagome Hollow-core Photonic Crystal Fibers for resonant rotation sensing. Opt. Commun. 2017, 383, 485-490. (13) Yan, D.; Popp, J.; Pletz, M.W.; Frosch, T. Highly Sensitive Broadband Raman Sensing of Antibiotics in Step-Index Hollow-Core Photonic Crystal Fibers. Acs Photonics. 2017, 4(1), 138-145. (14) Park, J.; Seo, J.; Jung, H.K.; Hyun, G.; Park, S.Y.; Jeon, S. Direct Optical Fabrication of Fluorescent, Multilevel 3D Nanostructures for Highly Efficient Chemosensing Platforms. Adv. Func. Mater. 2016, 26(39), 7170-7177. (15) Lova, P.; Bastianini, C.; Giusto, P.; Patrini, M.; Rizzo, P.; Guerra, G.; Iodice, M.; Soci, C.; Comoretto, D. Label-Free Vapor Selectivity in Poly(p-Phenylene Oxide) Photonic Crystal Sensors. Acs Appl. Mater. Inter. 2016, 8(46), 31941-31950. (16) Mariani, S.; Strambini, L.M.; Barillaro, G. Femtomole Detection of Proteins Using a Label-Free Nanostructured Porous Silicon Interferometer for Perspective Ultrasensitive Biosensing. Anal. Chem. 2016, 88(17), 8502-8509. (17) Xu, Y.S.; Zhang, X.P.; Luan, C.X.; Wang, H.; Chen, B.A.; Zhao, Y.J. Hybrid hydrogel photonic barcodes for multiplex detection of tumor markers. Biosens. Bioelectron. 2017, 87, 264-270. (18) Hu, X.X.; Wang, Y.Q.; Liu, H.Y.; Wang, J.; Tan, Y.N.; Wang, F.B.; Yuan, Q.; Tan, W.H. Naked eye detection of multiple tumor-related mRNAs from patients with photonic-crystal micropattern supported dual-modal upconversion bioprobes. Chem. Sci. 2017, 8(1), 466-472.

illustrated that the parathion was efficiently detected with the synthetic Au-MIP IO PCs from real samples.

Table 3 Recoveries of parathion from spiked water samples (n=5)

origin

tap water river water

parathion 0.01 ng/mL 0.1 µg/mL Recover RSD Recover RSD y(%) (%) y(%) (%)

-

96.3

4.0

101.5

3.6

-

95.5

4.9

98.7

4.5

Page 6 of 8

CONCLUSIONS In summary, a kind of Au-doped 3D photonic crystals (Au-MIP IO PCs) was well fabricated with surface molecularly imprinted technology for the determination of parathion. The Au-MIP IO PCs held fine optical properties and exhibited selected and specific response to the template molecule parathion. Even more, the parathion could be fast and efficient identified from real water samples. It is expected that the detected mode built with photonic crystals would facilitate a local determination for pesticides and environmental pollutants. ASSOCIATED CONTENT Supporting Information Supporting Information Available: The following files are available free of charge. The residue concentration after eluted 1~12 times with different content of EGDMA; SEM images of Au MIPs IO PCs after eluted 6 times, 9 times and 12 times AUTHOR INFORMATION

Corresponding Author * E-mail, [email protected]; tel/fax, +86-22-84655403. *E-mail, [email protected]; tel/fax, +86-22-84655191.

ORCID Xihao Zhang: 0000-0002-7481-9356

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS The authors thank the National Natural Science Foundation of China (Grant No. 81502847, 81472985, 81602896& AWS15J006), the Tianjin Research Program of Application Foundation and Advanced Technology (Grant No. 15JCYBJC51200) and the China Postdoctoral Science Foundation (2015M582848) for funding this research project.

Author Contributions All authors have given approval to the final version of the manuscript. #These authors contributed equally.

REFERENCES (1) Trinder, M.; McDowell, T.W; Daisley, B.A.; Ali, S.N.; Leong, H.S.; Sumarah, M.W.; Reid, G. Robiotic Lactobacillus rhamnosus

6 ACS Paragon Plus Environment

Page 7 of 8

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sensors (32) Wang, F.R.; Wang, J.D.; Sun, H.P.; Liu, J.K.; Yang, X.H. Plasmon-enhanced instantaneous photocatalytic activity of Au@Ag3PO4 heterostructure targeted at emergency treatment of environmental pollution. J Mater. Sci. 2017, 52, 2495–2510. (33) Wang, L.Y.; Chen, Y.C.; Lin, H.Y.; Hou, Y.T.; Yang, L.C.; Sun, A.Y.; Liu, J.Y.; Chang, C.W.; Wan, D.H. Near-IR-Absorbing Gold Nanoframes with Enhanced Physiological Stability and Improved Biocompatibility for In Vivo Biomedical Applications. ACS Appl. Mater. Interfaces 2017, 9, 3873−3884. (34) Sobral-Filho, R.G.; Brito-Silva, A. M. ; Isabelle, M.; Jirasek, A.; Lumbd, J.J; Brolo, A.G. Plasmonic labeling of subcellular compartments in cancer cells: multiplexing with fine-tuned gold and silver nanoshells. Chem. Sci. 2017, 8, 3038–3046. (35) Yu, F.; Li, Y.; Li, M.Y.; Tang, L.H.; He, J.J. DNAzyme-integrated plasmonic nanosensor for bacterial sample-to-answer detection. Biosens. Bioelectron. 2017, 89, 880-885. (36) Sun, X.L.; Wu, L.Y.; Ji, J.; Jiang, D.L.; Zhang, Y.Z.; Li, Z.J.; Zhang, G.Y.; Zhang, H.X. Longitudinal surface plasmon resonance assay enhanced by magnetosomes for simultaneous detection of Pefloxacin and Microcystin-LR in sea foods. Biosens. Bioelectron. 2013, 47, 318-323. (37) Lin, T.R.; Wu, Y.R.; Li, Z.H.; Song, Z.P.; Guo, L.Q.; Fu, F.F. Visual Monitoring of Food Spoilage Based on Hydrolysis-Induced Silver Metallization of Au Nanorods. Anal. Chem. 2016, 88, 11022−11027. (38) Mei, Z.; Tang, L. Surface-Plasmon-Coupled Fluorescence Enhancement Based on Ordered Gold Nanorod Array Biochip for Ultrasensitive DNA Analysis. Anal. Chem. 2017, 89, 633−639. (39) Xu, S.H.; Ouyang, W.J.; Xie, P.S.; Lin, Y.; Qiu, B.; Lin, Z.Y.; Chen, G.N.; Guo, L.H. Highly Uniform Gold Nanobipyramids for Ultrasensitive Colorimetric Detection of Influenza Virus. Anal. Chem. 2017, 89, 1617−1623. (40) Li, G.L.; Shi, Q.; Yuan, S.J.; Neoh, K.G.; Kang, E.T.; Yang, X.L. Alternating Silica/Polymer Multilayer Hybrid Microspheres Templates for Double-shelled Polymer and Inorganic Hollow Microstructures. Chem. Mater. 2010, 22(4), 1309–1317. (41) Fan, Z.X.; Zhang, H. Template Synthesis of Noble Metal Nanocrystals with Unusual Crystal Structures and Their Catalytic Applications. Accounts Chem. Res. 2016, 49(12), 2841-2850. (42) Zhou, C.H.; Wang, T.T.; Liu; J.Q.; Guo, C.; Peng, Y.; Bai; J.L.; Liu, M.; Dong, J.W.; Gao, N.; Ning, B.A.; Gao, Z.X. Molecularly imprinted photonic polymer as an optical sensor to detect chloramphenicol. Analyst 2012, 137(19), 4469-4474.

(19) Dong, Y.P.; Wang, J.; Peng, Y.; Zhu, J.J. Electrogenerated chemiluminescence of Si quantum dots in neutral aqueous solution and its biosensing application. Biosens. Bioelectron. 2017, 89, 1053-1058. (20) Chen, L.X.; Wang, X.Y.; Lu, W.H.; Wu, X.Q.; Li, J.H. Molecular imprinting: perspectives and applications. Chem, Soc. Rev. 2016, 45(8), 2137-2211. (21) Yoshikawa, M.; Tharpa, K.; Dima, S.O. Molecularly Imprinted Membranes: Past, Present, and Future. Chem. Rev. 2016, 116(19), 11500-11528. (22) De Middeleer, G.; Dubruel, P.; De Saeger, S. Characterization of MIP and MIP functionalized surfaces: Current state-of-the-art. Trac.-Trend. Anal. Chem. 2016, 76, 71-85. (23) Hou, J.; Zhang, H.C. ; Yang, Q.; Li, M.Z.; Jiang, L.; Song, Y.L. Hydrophilic-Hydrophobic Patterned Molecularly Imprinted Photonic Crystal Sensors for High-Sensitive Colorimetric Detection of Tetracycline. Small 2017, 11(23), 2738-2742. (24) Carboni, D.; Jiang, Y.; Faustini, M.; Malfatti, L.; Innocenzi, P. Improving the Selective Efficiency of Graphene-Mediated Enhanced Raman Scattering through Molecular Imprinting. Acs Appl. Mater. Inter. 2016, 8(49), 34098-34107. (26) Kairdolf, B.A.; Qian, X.M.; Nie, S.M. Bioconjugated Nanoparticles for Biosensing, in Vivo Imaging, and Medical Diagnostics. Anal. Chem. 2017, 89, 1015−1031. (27) Wang, P.L.; Lin, Z.Y.; Su, X.O.; Tang, Z.Y. Application of Au based nanomaterials in analytical science. Nano Today. 2017, 12, 64-97 (28) Liu, Y.; Zhou, H.B.; Hu, Z.W.; Yu, G.X.; Yang, D.T.; Zhao, J.S. Label and label-free based surface-enhanced Raman scattering for pathogen bacteria detection: A review. Biosens. Bioelectron. 2017, 94, 131-140. (29) Li, J.F.; Zhang, Y.J.; Ding, S.Y.; Panneerselvam, R.; Tian, Z.Q. Core−Shell Nanoparticle-Enhanced Raman Spectroscopy. Chem. Rev. 2017, 117, 5002−5069. (30) Qiu. G.Y.; Ng, S.P.; Liang, X.Y.; Ding, N,; Chen, X.F.; Wu, C.M.L. Label-Free LSPR Detection of Trace Lead(II) Ions in Drinking Water by Synthetic Poly(mPD-co-ASA) Nanoparticles on Gold Nanoislands. Anal. Chem. 2017, 89, 1985−1993. (31) Shrivas, K.; Nirmalkar, N.; Ghosale, A.; Thakura, S.S.; Shankarbc, R. Enhancement of plasmonic resonance through an exchange reaction on the surface of silver nanoparticles: application to the highly selective detection of triazophos pesticide in food and vegetable samples. RSC Adv., 2016, 6, 80739–80747.

7 ACS Paragon Plus Environment

ACS Sensors

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

TOC 128x136mm (300 x 300 DPI)

ACS Paragon Plus Environment

Page 8 of 8