Near-Infrared-Responsive Photoelectrochemical Aptasensing Platform

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Biological and Medical Applications of Materials and Interfaces

Near-Infrared Responsive Photoelectrochemical Aptasensing Platform Based on Plasmonic Nanoparticles Decorated Two Dimensional Photonic Crystals Zhenzhen Li, Xue Zhou, Jing Yang, Baihe Fu, and Zhonghai Zhang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b07128 • Publication Date (Web): 29 May 2019 Downloaded from http://pubs.acs.org on May 29, 2019

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ACS Applied Materials & Interfaces

Near-Infrared Responsive Photoelectrochemical Aptasensing Platform Based on Plasmonic Nanoparticles Decorated Two Dimensional Photonic Crystals Zhenzhen Li, Xue Zhou, Jing Yang, Baihe Fu, Zhonghai Zhang* Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Road, Shanghai 200241, China Table of Contents Graphic

ABSTRACT The photoelectrochemical (PEC) analysis is an emerging and fast developing biosensing technique. However, the in vivo PEC biosensing in deep tissue is seriously hampered due to the shallow penetration depth of ultraviolet and visible light. Expanding the optical absorption wavelength of photoelectrodes from visible light region into near infrared (NIR) light region is highly desirable due to its deep tissue penetrability and minimal invasiveness for organisms, but

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the exploration of facile strategy to implement efficient NIR absorption with good biocompatible is still challenging. Herein, a NIR PEC aptasensor is proposed by coupling plasmonic nanoparticles (NPs) into periodic two-dimensional nanocavities (NCs) photonic crystal as photoelectrodes, where the Au NPs are sputtered on periodic two-dimensional TiO2 NCs photonic crystal substrate to significantly enhance the NIR PEC response, and successfully achieve sensitive PEC detection of Hg2+ under irradiation of NIR light in blood. We believe the proposed NIR responsive Au/TiO2 NCs-based PEC aptasensor will open a new in vivo biosensing model for a series of important biomolecules and paves up an avenue for the practical applications of PEC biosensing in deep tissue or even in organs and brain of living body. KEYWORDS: near-infrared, photoelectrochemistry, photonic crystals, plasmonic resonance, aptasensor INTRODUCTION Photoelectrochemical (PEC) biosensing is an emerging and promising analytical strategy for biomolecules detection through integrating electrochemical and spectroscopy techniques with high sensitivity.1-8 However, the limited ultraviolet-visible (UV-vis) light response property of the photoelectrodes hinders its possibility for in vivo detection of target bio-molecules in deep tissue. To address this concern, expand-ing the optical absorption wavelength from UV light re-gion into near infrared (NIR) light region, with deep tissue penetrability and minimal invasiveness for organisms,9,10 will be an effective strategy for in vivo PEC bio-detection. Unfortunately, so far, only limit success has been achieved to accomplish NIR light response on PEC biosensing.11-15 Tang and co-authors have proposed a series of pioneering works with upconversion strategy for


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NIR PEC sensing,16,17 and the exploration of new strategy for extending the optical absorption of photoelectrodes from UV-vis into NIR region with a simple method is still highly desirable. Herein, a facile and novel strategy is proposed to fab-ricate NIR-responsive Au NPs on periodic two-dimensional TiO2 nanocavities (TiO2 NCs)-based photonic crystal substrate (Au/TiO2 NCs). The NCs, with highly or-dered periodicity, can be used as effective containers to uniformly distribute the Au NPs, and thus the high struc-tural and optical quality will implement the NIR light re-sponse with significantly enhanced light absorption activity. The Au/TiO2 NCs are further utilized as photoelectrode to fabricate PEC aptasensing platform through coupling aptamers as biomolecule recognition unit. In these PEC aptasensors, the Au NPs own both functions as light absorber for NIR response and as “anchor” to immobilize the aptamer on the surface through a unique Au-S linkage. The mercuric ion (Hg2+) is selected as target for PEC aptasensing in this work due to its highly toxic properties to cause a wide variety of diseases in brain, kidney, and central nervous system and other organs.18,19 Finally, the rationally designed PEC aptasensor will implement sensitive and selective detection of Hg2+ under illumination of NIR light, and provide the possibility for in situ detection in deep tissue, such as in blood vessel. RESULTS AND DISCUSSION The scheme of preparation approaches of Au/TiO2 NCs and fabrication processes of PEC aptasensors are illustrated in Figure 1a. The details for fabrication of Au/TiO2 NCs-based PEC aptasensors were described in Methods. In brief, the TiO2 nanotubes (Figure S1) were first fabricated by an electrochemical anodization method with Ti foil as precursor and substrate, then the as-grown amorphous nanotubes were ultrasonically removed in water, whereas left behind highly ordered NCs patterns on the Ti foil surface.20 The morphological structures of NCs were characterized by scanning electron microscopy (SEM) and were presented in Figure 1b1, where


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the Ti NCs with diameter of ~100 nm were clearly observed. Then, the Au NPs were sputtered into the NCs (Au/Ti NCs) as shown in Figure 1b2, and the as-sputtered Au NPs with size less than 10 nm were uniformly covered the NCs surface. Subsequently, the Au/Ti NCs underwent an annealing process in air to obtain the Au/TiO2 NCs photoelectrodes, and the size of Au NPs was swelled to ~25 nm (Figure 1b3). Both the size expansion of and spatial distribution of Au NPs are essential to implement efficient NIR light absorption.


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Figure 1. (a) Schematic diagram of fabrication processes of Au/TiO2 NCs-based PEC aptasensors; SEM images of (b1) Ti NCs, the inset is enlarged SEM image of Au NPs in cavity, (b2) Au/Ti NCs, and (b3) Au/TiO2 NCs; (c) UV/Vis/NIR diffuse absorption spectra; FDTD simulation of electric field distributions of (d1) single NC and (d2) Au NPs in NC. The optical properties of Ti NCs, Au/Ti NCs, TiO2 NCs (Ti NCs underwent annealing process without Au NPs), and Au/TiO2 NCs were presented in Figure 1c. The Ti NCs did not show significant absorbance in whole spectral region, whereas, after annealing process, the TiO2 NCs displayed strong optical absorption with central peak at wavelength of 500 nm, which indicated that both the crystallinity and periodic nanostructure of NCs contributed the high quality of photonic materials. In addition, Au/Ti NCs also did not provide clear enhancement of optical absorption. Very interestingly, the Au/TiO2 NCs not only maintained the photonic absorption in visible light region with the same peak wavelength to TiO2 NCs, implied the similar NCs diameter and periodicity, but also presented new plasmonic peak in NIR region. In addition, the plasmonic resonance wavelength can be easily tuned through adjusting the sputtering time of Au NPs and annealing temperatures (Figure S2). The optimized central peak wavelength of 760 nm was rationally located in the spectral region of NIR light source used in this work. Furthermore, finitedifference-time-domain (FDTD) simulations were performed to support the enhancement of optical absorption. As presented in Figure 1d, the light was first trapped in the NCs, and then shrank on the surface of Au NPs with further enhance light absorption after introducing Au NPs into the NCs, which contributed efficient NIR light response. Finally, the aptamers were anchored to the Au/TiO2 NCs through the unique Au-S bonds to assemble the PEC aptasensors. In this work, the aptamer of 5’-HS–(CH2)6–TTT TTT TTT TTT TTT TTT-3’ was selected to specially binding with Hg2+,21 in addition, other aptamers also can be utilized for different detection targets, and thus to establish a versatile PEC aptasensing platform.


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The structural and chemical analysis of Au/TiO2 NCs were performed to understand the importance of sputtered Au NPs. The crystalline structures were analyzed by x-ray diffraction (XRD) measurement and the XRD patterns are presented in Figure 2a. The diffraction peaks of Ti NCs can be ascribed to metallic Ti (JCPDS no. 44-1294) patterns, which indicated that the chemical composition of Ti NCs was metallic Ti or amorphous oxides. The Au/Ti NCs presented very similar XRD patterns to Ti NCs with an additional weak Au (200) peak due to the sputtered Au NPs with small size. In addition, after annealing process, the new rutile TiO2 (110) peak can be observed in TiO2 NCs and Au/TiO2 NCs samples, and more importantly, obvious Au (200) and (220) peaks emerged in Au/TiO2 NCs, implied the size growth and crystallinity improvement of Au NPs in the annealing process.

Figure 2. (a) XRD patterns, (b) Raman spectra, (c) core-level XPS of Ti 2p, and (d) core-level XPS of Au 4f of (i) Ti NCs, (ii) Au/Ti NCs, (iii) TiO2 NCs, and (iv) Au/TiO2 NCs.


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The Raman spectra were also recorded to examine the vibrational behaviour of the Au/TiO2 NCs and are presented in Figure 2b. Before annealing, the Ti NCs and Au/Ti NCs showed two vibrational models in 855 cm-1 and 1035 cm-1, which can be ascribed to Ti-O stretching vibration of TiO4 tetrahedral and Ti related defect sites in amorphous titanates.2224

After annealing, the typical Raman bands in 443 cm-1 and 606 cm-1, ascribed to B1g and

A1g vibration of rutile TiO2,25,26 can be clearly observed in TiO2 NCs and Au/TiO2 NCs. In addition, all samples presented large luminescence background at 1000-2000 cm-1,11 implied the formation of disordered defects. While, after sputtering of Au NPs, the luminescence background in Au/TiO2 NCs further enhanced, which can be ascribed to the increase of defect sites due to the bombardment from the high energy of Au ion in the sputtering process.4 Further characterization of surface analysis on these samples, X-ray photoelectron spectroscopy (XPS) technique were performed to determine the surface chemical compositions and corresponding nature of chemical microenvironment.27 All four samples showed clear Ti and O elements from the XPS survey spectra (Figure S3), and the Au element was detected in Au/Ti NCs and Au/TiO2 NCs. The core-level Ti 2p XPS was presented in Figure 2c. For Ti NCs, the strong peaks at 458.7 eV and 464.4 eV can be ascribed to Ti 2p3/2 and Ti 2p1/2 of TiO2,3,28 and the weak peaks at 453.5 eV, 454.2 eV, and 459.1 eV can be as-signed to metallic Ti and non-stoichiometric titanium oxides.29,30 After decoration of Au NPs, the binding energy of Ti 2p3/2 and Ti 2p1/2 positively shifted to 459.3 eV and 465.0 eV, which indicated that the electron transfers between Au NPs and Ti NCs. After annealing, the TiO2 NCs showed typical binding energy at 458.6 eV and 464.4 eV for Ti 2p3/2 and Ti 2p1/2 of rutile TiO2. Compared to TiO2 NCs, the Au/TiO2 NCs also


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displayed binding energy shift to positive direction of 459.3 eV and 465.0 eV, further proved the effective electron transfers between Au NPs and TiO2 NCs. The core-level XPS of O 1s was also recorded in Figure S4, in which the binding energy shift phenomena in the annealing and sputtering processes can be detected, further helped to confirm the potential charge transfer. Finally, the core-level Au 4f XPS was well fitted with binding energy of 84.6 eV and 88.2 eV for Au 4f7/2 and Au 4f5/2 respectively in Figure 2d, which can be attributed to metallic Au.31 After annealing, the Au 4f core level XPS for Au/TiO2 NCs showed a negatively shift of binding energy of 84.2 eV and 87.8 eV for Au 4f7/2 and Au 4f5/2 respectively, which implied that the annealing process further reinforced the connection between the TiO2 NCs and Au NPs, thus subsequently activated the electron transfer at their interfaces. All these characterization results indicated the successful formation of Au/TiO2 NCs, revealed the crystal structure changes, and predicted the electronic structure modifications in the annealing and sputtering processes.


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Figure 3. (a) I-t measurements on Ti NCs, Au/Ti NCs, TiO2 NCs, and Au/TiO2 NCs; (b) IPCE plots of TiO2 NCs and Au/TiO2 NCs; (c) Electrochemical impedance spectra of Nyquist plots of TiO2 NCs and Au/TiO2 NCs in dark and under NIR light illumination, inset is the magnified Nyquist plots of Au/TiO2 NCs in dark and under NIR light illumination; (d) Mott-Schottky plots of TiO2 NCs and Au/TiO2 NCs. The PEC activity of Au/TiO2 NCs photoelectrodes were estimated under illumination of NIR light. As presented in Figure 3a, the Ti NCs, Au/Ti NCs, and TiO2 NCs showed insignificant photocurrent response. While, the Au/TiO2 NCs showed a superior photocurrent response, which can be ascribed to the contribution of NIR plasmonic resonance of Au NPs in NIR region, hence boosted the injection of hot electron from Au NPs into the conduction band of TiO2. In addition, the sputtering time of Au NPs and annealing temperatures have also been optimized to 30 seconds and 500 °C (Figure S5). Shorter or longer of sputtering time resulted in the decrease of photocurrent density due to the excess aggregation or un-uniform


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distribution of Au NPs (Figure S6), what’s more, the lower annealing temperature also did not present good photocurrent density due to the insufficient accumulation of Au NPs (Figure S7), while, higher annealing temperature would damage the periodic structure of NCs (Figure S8). Furthermore, the Au NPs deposited on flat TiO2 film was also fabricated, and the micromorphology was presented in Figure S9a, where the Au NPs were over aggregated without the separation of TiO2 NCs, and thus did not presented obvious NIR photocurrent response (Figure S9b). To better understand the increased PEC activity in NIR region, the incident-photon-tocurrent-conversion efficiency (IPCE) measurements were performed on the TiO2 NCs and Au/TiO2 NCs.32 The IPCE values were calculated using the following equation:33 IPCE (%) = 1240I/λJlight × 100%

(1)

where I is photocurrent density (mA cm-2), Jlight is the irradiance (mW cm-2) of incident light, and λ is the wavelength (nm) of incident light. As presented in Figure 3b, the TiO2 NCs did not show any photo-response in NIR region. The high IPCE response in near ultraviolet region can be ascribed to the intrinsic excitation of TiO2, and the low IPCE value in visible light region can be ascribed to excitation of intra-bands due to the surface defects. Different from TiO2 NCs, the Au/TiO2 NCs exhibited considerable enhancement of PEC performance both over visible and NIR regions, which results further revealed the plasmonic resonance mechanism for NIR PEC response.


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Electrochemical impedance and capacitance measurements were further employed to uncover the electronic structure information of Au/TiO2 NCs. As shown in Figure 3c, compared to TiO2 NCs, the Au/TiO2 NCs presented much smaller resistance. In addition, the Au/TiO2 NCs showed much smaller arc in the Nyquist plots under illumination of NIR light than in dark, which further confirmed its NIR response properties. The Mott-Schottky electrochemical capacitance measurements have also been conducted to estimate the electronic properties of the Au/TiO2 NCs. The Mott−Schottky plots were collected with frequency of 5 kHz to determine the semi-conductive properties and carrier density (ND) of TiO2 NCs and Au/TiO2 NCs using the below equation:34 1 𝐶2

=

2

[(𝑈𝑆 ― 𝑈𝐹𝐵) ―

𝑁𝐷𝑒𝜀𝜀0

𝑘𝐵𝑇 𝑒

]

(2)

where C is the space charge capacitance in the semiconductor, ND is the electron carrier density, e the is elementary charge value, ε0 is the permittivity of the vacuum, ε the is relative permittivity of the semiconductor, Us is the applied potential, T is the temperature, and kB is the Boltzmann constant.6 Figure 3d presented the Mott−Schottky plots as 1/C2 vs potential, and both the slopes of the linear part of the curves of TiO2 NCs and Au/TiO2 NCs were positive, indicating the maintaining of n-type semi-conductive property after loading of Au. In addition, the Au/TiO2 NCs presented lower slope value than TiO2 NCs, implied the increased of carrier density, which was beneficial for the fast electron transfer and partially contributed to enhancement of PEC response.


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Figure 4. (a) Amperometric transient plots of the Au/TiO2 NCs-based PEC aptasensors under illumination of NIR light with different concentrations of Hg2+; (b) Calibration curve of the Au/TiO2 NCs-based PEC aptasensors; (c) Selectivity of the Au/TiO2 NCs-based PEC aptasensors for Hg2+ detection; (d) Practical application of real sample detection in fetal bovine serum.

The PEC aptasensing performance were conducted with Hg2+ as target. The aptamer of Trich oligonucleotides specially binding to Hg2+ through the formation of T-Hg2+-T,35 and changed spatial structure of aptamer from single strand to double strands and hairpin structures, thus inhibited the photocurrent density due to the increased steric effects.36 As presented in Figure 4a, the NIR photocurrent response decreased with the increase of Hg2+ concentrations, and a linear calibration was obtained between the photocurrent density and the logarithm of Hg2+ concentrations in the range from 10 fM to 10 nM (Figure 4b) with a low


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detection limit of 3.3 fM (S/N = 3), which value was comparable to the best Hg2+ sensors (Table S1). Good selectivity ensures high accuracy. Therefore, anti-interference is another important factor for analysis applications. As shown in Figure 4c, the 1 pM of Hg2+ resulted in a significant NIR PEC response, whereas other interference metal ions with concentration of 1.25 nM still cannot cause observable NIR PEC changes. After adding these interference ions, another 1 pM Hg2+ was added, and an obvious NIR photocurrent decrease was observed again, in addition, after added the mixture of Hg2+ and interference metal ions, as expected, a significant and similar NIR photocurrent can be also obtained. All of these measurements helped to reveal the good selectivity of the Au/TiO2 NCs based-PEC aptasensors. It was worth mentioning that compared with other methods, the PEC aptasensing in this study was performed under illumination of NIR light, which can ensure the deep tissue penetration and innocuousness to the detection targets. Therefore, the practical application of the PEC aptasensor was investigated by detecting Hg2+ in fetal bovine serum. As presented in Figure 4d, the concentration of Hg2+ in fetal bovine serum can be measured to be ~50 fM. These experimental results manifested that the proposed NIR responsive PEC aptasensor presented good potential to implement in vivo detection of important biomolecules in deep tissue and even in organs or in brain. CONCLUSION


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In summary, a new strategy for extending the plasmonic absorption of Au NPs into NIR region was proposed. The Au NPs were sputtered on periodic two-dimensional TiO2 NCs photonic crystal substrate to implement efficient NIR light response. Both the size expansion of and spatial distribution of Au NPs were essential to enhance the NIR light absorption. The Au/TiO2 NCs were further utilized as photoelectrode to fabricate PEC aptasensing platform and successfully realized the sensitive and selective PEC detection of Hg2+ under illumination of NIR light in blood. More importantly, the deep tissue penetrability and minimal invasiveness for organisms of NIR light provided promising potentials for in vivo PEC biosensing of other biomolecules through the proposed PEC aptasensing platform and paved up an avenue for the practical applications of PEC biosensing in deep tissue or even in organs and brain of living body. METHODS Materials. Ethylene glycol (EG), ammonia fluoride (NH4F), tris(2-carboxyethyl)-phosphine (TCEP), Tris-HCl buffer solution (pH 7.4,10 mM), 6-mercapto-1-hexanol (MCH), and potassium chloride (KCl), were purchased from Macklin Inc, Shanghai, China. Hg(NO3)2 was supplied by Guobiao (Beijing) Testing & Certification Co., Ltd. All other reagents were of analytical grade and used as received. Thiol terminated Hg2+ binding DNA aptamer (5′-HS–(CH2)6–TTT TTT TTT TTT TTT TTT-3′) was obtained from Sangon Biotech, Shanghai, China. Fetal bovine serum was obtained from Procell Life Science & Technology Co, Ltd. Wuhan China. Material Characterization. The scanning electron microscopy (SEM; Hitachi S4800) was used to characterize the morphologies of electrodes. The spectrophotometer (Shimadzu, UV 3600) was


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used to record the diffuse absorption UV-vis spectra with BaSO4 powder as reference. The crystalline structure of the electrodes was analyzed by X-ray diffraction (XRD) on a Bruker D8 Discover diffractometer. The DXR Raman Microscope (Thermo) with excitation of 532 nm laser was used to record the Raman spectra. The X-ray photoelectron spectroscopy (XPS) was performed on an Axis Ultra instrument (Kratos Analytical) with a monochromatic Al Kα X-ray source. Preparation of Au/TiO2 NCs photoelectrode. The TiO2 NCs were fabricated with a one-step anodization process coupled with an annealing process. The anodization was carried out using a two-electrode electrochemical system with the Ti sheet as anode and Pt foil as cathode, respectively. The NH4F (0.5 wt %) was dissolved in EG solution with small amount of water (2 v/v %), and all the anodization experiments were carried out at room temperature. The voltage used for the anodization is 60 V, and the duration is 30 min. After anodization, the as-grown nanotubes were all ultrasonically removed. The Au NPs were sputtered onto the obtained TiO2 NCs by an ion-sputtering instrument (JS-1600, Beijing Saintins Technology Co., Ltd.) with vacuum degree of 0.1 mbar and sputtering current of 6 mA. The deposited Au amount can be adjusted through tuning the sputtering time, and the optimized sputtering time was 30 seconds. Finally, the Au loading on the TiO2 NCs was annealed in air at different temperatures. Fabrication of PEC aptasensors. First, TCEP was used to break the S-S bond of the thiolated aptamer, and 1mL of Hg2+ aptamer (5 μM) solution was activated by 20 μL TCEP (10 mM) for 1 h.37 The Au/TiO2 NCs was incubated with the aptamer in TCEP solution. In order to ensure the strength of the Au-S bond, the mixture was gently mixed for 16 h. Next, the photoelectrode was immersed in 1 mM MCH for 1 h to inhibit the nonspecific adsorption and being washed then stored at 4 °C for further sensing applications.


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Performance of the PEC aptasensors. The PEC activity of the Au/TiO2 NCs were estimated in a three-electrode configuration with the Au/TiO2 NCs, Ag/AgCl and Pt foil as working, reference and counter electrodes, respectively. The Tris-HCl buffer solution (pH 7.4,10 mM) was used as supporting electrolyte. The detection potential used for PEC sensing was 0 V vs Ag/AgCl under the NIR light illumination. The electrochemical impedance spectra (EIS) were measured with an excitation signal of 10 mV amplitude in a PGSTAT 302N Autolab Potentiostat/Galvanostat (Metrohm). Afterward, Mott-Schottky measurement was performed at fixed frequency of 5 kHz. The IPCE measurements were conducted with a monochromatic system (model 74125, Newport). ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.xxxxxxx. Experimental section, SEM images of TiO2 nanotubes, DRS of samples annealed with different temperatures, XPS survey and core-level XPS of O 1s, additional measurements, and SEM images of controlled samples. AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] ACKNOWLEDGMENT We appreciate the support from National Natural Science Foundation of China (No. 21822403, 21775045). REFERENCES


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Near-Infrared-Responsive Photoelectrochemical Aptasensing Platform

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