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Abstract
It is very vital to construct the dense hot spots for the strong surface-enhanced Raman scattering (SERS) signals. We take full advantage of the MoS2 edge-active sites induced from annealing the Ag film on the surface of the MoS2. Furthermore, the composite structure of Au-Ag bi-metal nanoparticles (NPs)/MoS2 hybrid with pyramid structure is obtained by the in situ grown AuNPs around AgNPs, which serves the optimal SERS performance (enhancement factor is ~9.67 × 109) in experiment. Due to the introduction of AuNPs with the simple method, the denser hot spots contribute greatly to the stronger local electric field, which is also confirmed by the finite-different time-domain (FDTD) simulation. Therefore, the ultralow limit of detection (the LOD of 10−13 and 10−12 M respectively for the resonant R6G and non-resonant CV), quantitative detection and excellent reproducibility are achieved by the proposed SERS substrate. For practical application, the melamine molecule is detected with the LOD of 10−10 M using the proposed SERS substrate that has the potential to be a food security sensor.
© 2018 Optical Society of America under the terms of the OSA Open Access Publishing Agreement
1. Introduction
MoS2, a representative 2D material, with the virtue of remarkable characteristics such as high surface area and tunable band gap has been researched and investigated widely to exploit its potential for the field-effect transistors [1], optical detectors [2], capacitors [3,4] and sensors [5,6]. It has also been demonstrated that tunable plasmon dispersion can be achieved deriving from the electronic and optical properties, which is a desirable candidate for the plasmonic sensor [7], such as surface plasmon resonance (SPR) [8] and surface-enhanced Raman scattering (SERS) senor [9]. Especially, the research on the MoS2-based SERS has attracted extensive interests. Although the SERS substrates with various forms have been designed and proposed [10–15], it is still a change to fabricate the SERS substrate with excellent activity and performance.
Recently, hybrids of MoS2 and metal nanoparticles (NPs) have been designed and exhibited interesting SERS activity, where the MoS2 can serve as an ideal supporting layer to stabilize the metal NPs. To synthesize these hybrids, a variety of strategies have been attempted. For example, with the assist of the physical deposition, one can successfully obtain the metal NPs decorated MoS2 with this ex-situ growth method, where additional species cannot be introduced [16,17]. With the traditional focused continuous laser beam approach, Au-MoS2 hybrid can be fabricated in an in situ growth method by inducing chemical activity of MoS2 [18]. However, due to the intense heating effect introduced by the laser, the surface of the hybrid will be thermally oxidized. Although by changing the continuous laser beam to the temporally shaped femtosecond pulses, AuNPs with various shapes can be in situ assembled on the MoS2 [9]. Whereas, the SERS activity of this Au-MoS2 hybrid can be further enhanced as only one metal is adopted here.
As we all known, there are two generally accepted mechanisms for SERS, i.e, electromagnetic mechanism (EM) on the noble metal nanostructure and the chemical mechanism (CM) introduced by the 2D material [19]. Mostly, the enhancement induced by the former is greatly larger than that of the latter. And nanostructures of Ag, Au and Cu are widely chosen to be excited and produce the surface plasmons. Thereinto, as the SPR of the Ag and Au can be exited by the visible light, SERS substrates based on these two metal are typically developed. Compared with single metal SERS substrate, the Au/Ag bi-metal substrate can generate a larger number of the hot spots and can detect both resonant and non-resonant molecule by virtue of the tunable and wide SPR band [20]. This strategy provides us a capital idea to improve the SERS enhancement of the based MoS2 substrate.
Besides, one can also further enhance the SERS signal by designing and transferring the substrate form 2D planar structure to the 3D structure such as silicon nanowire [21], pyramid structure [22] and so on. With the advantage of the large specific surface area, the optical field on the 3D substrate can be effectively amplified, which will increase the region of the hot spots and is much beneficial for the assembling of molecular. Consequently, even under ultra-low concentration, the SERS signal can still be observed on these 3D SERS substrates.
In this work, we present a method to introduce and tune the edge-active sites of the MoS2 for the in situ fabrication of AuNPs by annealing the Ag film on the surface of the MoS2. With this facile method, we can successfully prepare the Au-Ag bi-metal NPs/MoS2 hybrid with pyramid structure as active SERS substrate for both resonant and non-resonant detection. The thermally annealed AgNPs can endow the MoS2 with chemical reduction ability by introducing the edge-active sites, which can decorate the AuNPs on the modified MoS2 in HAuCl4 solution. Using the R6G and CV respectively as the resonant and non-resonant molecule, we demonstrated the proposed Au-Ag bi-metal NPs/MoS2 hybrid possessing high enhancement, well stability and reproducibility in experiment. The detection limits of this Au-Ag bi-metal NPs/MoS2 hybrid pyramidal SERS substrate are 10−13 M and 10−12 M respectively for the resonant R6G and non-resonant CV. Here, the outstanding SERS performance can be assigned to the following aspect: 1) the strong couple of the board SPR band of Au-Ag bi-metal NPs with the exciton in MoS2 will greatly enhance the SERS signal based on the EM [23,24]. 2) The 3D pyramid structure of the proposed SERS substrate will effectively amply the optical field around the AuNPs-AgNPs and increase the region of the hot spots. 3) The MoS2 can further introduce the enhancement based on the CM and assemble molecular on the surface benefited from the merit of the good biocompatibility [25,26]. The active SERS performance of the proposed substrate was also verified in theory with the FDTD method.
2. Experimental setup
2.1 Fabrications of Au-Ag bi-metal NPs/MoS2 hybrid pyramidal SERS substrate
The pyramid Si was prepared with a wet etching method as reported in our previous work [27]. After that, uniform MoS2 was grown on the obtained pyramid Si substrate through a thermal decomposition method. Here, (NH4)2MoS4 with the purity of 99.99%, as the precursor, was spined on the pyramid Si and annealed twice in 500°C for 30 min and 800°C for 60 min, which is much conducive to the achievement of the high-quality MoS2. Following that, Ag film was deposited on the MoS2/pyramid Si substrate using thermal evaporation process and annealed at 500°C for 30 min to dewet into the AgNPs/MoS2 hybrid, which is much crucial for modifying the MoS2 with edge-active sites. Then to fabricate the Au-Ag bi-metal NPs/MoS2 hybrid pyramidal SERS substrate, the modified AgNPs/MoS2 hybrid was immersed in HAuCl4 with concentration of 0.01mM for 1min, where AuNPs can be in situ deposited on the edge-active sites.
2.2 Apparatus and characterization
The morphologies of the prepared samples were characterized by the scanning electron microscope (SEM ZEISS Sigma 500) assistant with energy dispersive spectrometer (EDS). Transmission electron microscope (TEM JEM-2100) was also carried out to investigate the characteristic of the sample. We carried out the X-ray photoelectron spectroscopy (XPS Thermo Scientific Escalab 250Xi) measurements to confirm the formation of the edge-active sites on the MoS2 film after the annealing process.
2.3 SERS spectra measurement
To study the SERS behaviors of the proposed Au-Ag bi-metal NPs/MoS2 hybrid pyramidal SERS substrate, we chose the Raman spectrometer (Horiba HR Evolution 800) with the excited laser of 532 nm to collect the SERS spectra and maintained all the parameters invariant throughout all the SERS experiments.
3. Results and discussions
We characterized the surface morphologies of samples obtained from each step of the preparation process as shown in Fig. 1. As shown in Fig. 1(a), MoS2 thin film covers completely on the surface of pyramid Si except for a few broken area (red dash circle) in the valley bottom, which can be attributed to the unavoidable and heterogeneous distribution of the precursor for the formation of the MoS2 especially in region of the valley bottom. The Raman spectrum of MoS2 (red curve) as shown in Fig. 1(d) obviously exhibits the characteristic peaks of MoS2 at ~378 and 405 cm−1 respectively named as and A1g assigned to the opposite vibrations of two S atoms with its connected Mo atom and the out-of-plane vibration of S atoms in opposite directions [28], which confirms the multilayer MoS2 film was successfully fabricated on the pyramid Si. Following that, the Ag hemispheric nanoparticles were deposited on the MoS2/pyramid Si substrate [(Fig. 1(b)]. The size of AgNPs could be counted by nanomeasure software as presented in the inset in Fig. 1(b) and the average diameter is about 48 nm. The Raman spectrum of MoS2 (green curve) on the obtained AgNPs/MoS2/pyramid Si substrate was also collected again in Fig. 1(d). It is noteworthy that the obvious frequency shift of and A1g peaks can be observed [28], which can be attributed to the formation of the edge-active sites on the MoS2 during the dewet process from Ag film to AgNPs [9], and is expected to be much beneficial for the in situ growth of AuNPs on these edge-active sites of the MoS2. Furthermore, when the obtained substrate reacting with HAuCl4 solution, some bright nanoparticles appear around AgNPs as presented in Fig. 1(c). Combined with the energy dispersive spectrometer (EDS) mapping illustrated in Fig. 2, we can identify that the larger nanoparticles can be assigned to the existence of the AgNPs and the denser distribution of Au element compared to Ag element can be attributed to the formation of the AuNPs during the reaction between HAuCl4 and MoS2 on the edge-active sites. As the inset in Fig. 1(c), the average diameter of these AuNPs on the surface of the AgNPs is ~11 nm. Besides, we can also observe relatively rare S element, which may be attributed to the existence of the MoS2 defects. To clearly observe the well distribution and identify the size of AuNPs, the TEM characterization of the as-synthesized AuNPs-AgNPs/MoS2 was carried out in Fig. 1(e), where we can observe that the AuNPs not only grow around AgNPs but also grow on the edge-active sites of MoS2 introduced by the AgNPs dewet process (see the inset). The inset also shows the obtained multilayer MoS2 and the average diameter of AuNPs formed on the edge-active sites is about 5 nm. The EDS was measured to confirm the composition of elements especially including Au, Ag, S and Mo [Fig. 1(f)]. The elements (S and Mo) come from the MoS2 film, and the Ag element is evaporated and annealed on the surface of MoS2. Therefore, the MoS2 defect is developed to form AuNPs during the reaction with HAuCl4, where Au element comes from. Compared to the pristine MoS2 without the deal of the annealing process, only few AuNPs were obtained on the pristine MoS2/pyramid Si substrate, as demonstrated in Fig. 3, after reacting with HAuCl4 solution under the same condition as the case of the former. The Raman peaks ( and A1g) as interior label (blue curve) in Fig. 1(d) also shows the the frequency shift and demonstrates the enhancement of SERS performance compared with that collected on the MoS2/pyramid Si and AgNPs/MoS2/pyramid Si [28], which can be attributed to the denser hot spots from the participation of AuNPs with the help of the edge-active sites inducing from annealing the Ag film on the surface of the MoS2.
Fig. 1 SEM morphology characterization respectively from (a) MoS2/pyramid Si, (b) AgNPs/MoS2/pyramid Si and (c) AuNPs-AgNPs/MoS2/pyramid Si substrate. (d) SERS spectra of MoS2 on MoS2/pyramid Si, AgNPs/MoS2/pyramid Si and AuNPs-AgNPs/MoS2/pyramid Si substrate. (e) TEM image of the synthesized AuNPs-AgNPs/MoS2, and (f) the corresponding EDS spectrum.
Fig. 2 EDS elemental maps from (b) Si, (c) S, (d) Mo, (e) Ag and (f) Au on the (a) AuNPs-AgNPs/MoS2/pyramid Si substrate.
Fig. 3 The SEM morphology of AuNPs/MoS2/pyramid Si obtained from the reaction of MoS2/pyramid Si and HAuCl4.
In order to further prove the defect of MoS2 generating the edge-active sites supporting the in situ growing of AuNPs, the XPS characterizations were carried out to qualitatively and quantificationally analyze the chemical composition of elements (Mo, S and Ag) in the fabricated substrates (AgNPs/MoS2/pyramid Si and MoS2/pyramid Si) as exhibited in Fig. 4. Figure 4(a) shows the XPS survey spectrum obtained from AgNPs/MoS2 on pyramid Si substrate. Therefore, the following elements, Mo 3d and S 2p from MoS2 film and Ag 3d from AgNPs, were detected. Among this, the detailed Ag 3d XPS spectrum is exhibited in the inset of Fig. 4(a), which demonstrates the peaks at ~374 eV and ~368 eV are attributed to Ag 3d3/2 and Ag 3d5/2, respectively. As a contrast, the full XPS spectrum from MoS2/pyramid Si substrate is shown in Fig. 5. In Fig. 4(b), the two peaks at ~229 eV and ~232 eV are attributed to Mo4+ 3d5/2 and Mo4+ 3d3/2 from MoS2 film, respectively. The peak (~236 eV) with the weak intensity is assigned to Mo6+ that is induced from MoO3. But the intensity of this peak is attenuate after the annealing process of Ag film. And noted that there is a movement (~0.79 eV) for the peak assigned to S 2s, which illustrates the MoS2 defect ascribed to the generation of lattice distortion together with the annealing [24]. Figures 4(c) and 4(d) present the detailed S 2p XPS spectra analysis respectively obtained from AgNPs/MoS2/pyramid Si and MoS2/pyramid Si. As we all know, the two peaks at ~162.3 eV and ~163.8 eV are attributed to S 2p3/2 and S 2p1/2 from the S2-. Compared to that of on MoS2/pyramid Si substrate, a fresh peak at 161.7 eV certifies the low binding energy 2nd feature attributed to MoS2 defect [29]. Therefore, the MoS2 defect generated from the participation of AgNPs can be effectively used as the edge-active sites to grow the AuNPs on the interface between AgNPs and MoS2, which will contribute to excite the more hot spots and be much beneficial to achieve the highly sensitive SERS signals.
Fig. 4 (a) XPS survey spectrum obtained from AgNPs/MoS2 on pyramid Si substrate. Inset: Detailed Ag 3d XPS spectrum analysis. (b) Detailed Mo 3d XPS spectra of core-level peaks of MoS2 on AgNPs/MoS2/pyramid Si (red curve) and MoS2/pyramid Si (blue curve). Detailed S 2p XPS spectra analysis respectively from (c) AgNPs/MoS2/pyramid Si and (d) MoS2/pyramid Si.
In order to demonstrate the superiority of introducing AuNPs to AgNPs/MoS2/pyramid Si utilizing the MoS2 defect in terms of SERS performance, R6G, as a frequently-used resonant molecule, was respectively detected on the AuNPs-AgNPs/MoS2/pyramid Si, AgNPs/MoS2/pyramid Si and MoS2/pyramid Si substrate using the Raman spectrometer with 532 nm laser. As shown in Fig. 6(a), the SERS signals of each vibrational modes of R6G (10−5 M) from the AuNPs-AgNPs/MoS2/pyramid Si substrate are much higher than that on the other two bases. The relative intensity of the characteristic peaks at 613, 774 and 1363 cm−1 corresponding to the above substrates was collected to plot the histogram as illustrated in Fig. 6(b). Obviously, the optimal SERS performance can be obtained from the AuNPs-AgNPs/MoS2/pyramid Si substrate, which can be attributed to introduction of AuNPs. Therefore, the synergistic effects of AuNPs, AgNPs and MoS2, that combine the strong interparticle near field coupling effect and the sharp plasmonic peak as well as the the strong coupling between plasmonic resonances and excitons [as demonstrated by the photoluminescence (PL) spectrum in Fig. 7(a)], will contribute to the stronger electric fields enhancement induced from the denser hot spots under the excitation of laser. For the case of MoS2, the SERS signal of molecules is enhanced mainly due to CM, which shows the weaker intensity. To further reveal the advantage of the proposed SERS substrate, the local electric field distribution was calculated using the finite-different time-domain theoretical simulation. According to the schematic of AuNPs-AgNPs in Fig. 6(c), the diameter of AgNPs was set as 48 nm and the diameter of AuNPs around AgNPs and on the surface of AgNPs was respectively set as 5 nm and 11 nm, and all the spaces between the adjacent nanoparticles were set as 1.5 nm. The laser of 532 nm wavelength was chosen in this simulation. Just as we all expected, the dense hot spots mainly distribute in the nanogaps between the AgNPs and AuNPs respectively generated from the edge-active sites of MoS2 and AgNPs reacting with HAuCl4 as illustrated in Figs. 6(d) and 6(e), and the nanogaps between the adjacent AuNPs as presented in Fig. 6(f). Therefore, combined with the extinction spectra of the bi-metal [Figs. 7(b), 7(c) and 7(d)] the theoretical results demonstrate the strong electric fields enhancement is excited on the proposed substrate and is consistent with the experiment, which will contribute to enhance the SERS signals of the traditional molecules.
Fig. 6 (a) Raman spectra of R6G molecules (10−5 M) detected on the AuNPs-AgNPs/MoS2/pyramid Si, AgNPs/MoS2/pyramid Si and MoS2/pyramid Si substrate. (b) The collected intensity of the characteristic peaks (613, 774 and 1363 cm−1) corresponding to the above substrates. (c) Schematic of AuNPs-AgNPs structure for FDTD theoretical simulation. The local electric field distributions respectively from (d) x y (the center of the smaller AuNPs), (e) x z and (f) x y (the center of the bigger AuNPs) cross-section polarized along the x direction.
Fig. 7 (a) The PL spectrum of MoS2 and Au-Ag bi-metal NPs/MoS2. The extinction spectra respectively for the (b) Ag, (c) Au and (d) bi-metal.
The resonant and non-resonant molecules R6G and CV are respectively employed to evaluate the SERS performance of the elaborate Au-Ag bi-metal NPs/MoS2 hybrid pyramidal SERS substrate. SERS spectra of R6G on the SERS substrate ranging from 10−5 M to 10−13 M were collected in Fig. 8(a). The intensity of the representative peaks at 613 and 774 cm−1 respectively assigned to C-C-C ring in-plane and C-H out-of-plane bending mode is relatively strong and is still recognized even with ultralow concentration of 10−13 M for R6G. The peak at 1187 cm−1 is assigned to C-H in-plane vibrational mode and the other peaks (1363, 1509 and 1651 cm−1) of R6G are all assigned to aromatic C-C stretching mode, which are consistent with the previous work [30]. The excellent sensitivity of the as-synthesized substrate can be attributed to the dense hot spots generated from the ultranarrow nanogaps supported by the composition of bi-metal and the in situ growing AuNPs. The SERS enhancement factor of Au-Ag bi-metal NPs/MoS2 hybrid pyramidal structure for R6G molecules is calculated by the standard equation [30]:
Fig. 8 (a) Raman spectra of R6G (the concentration from 10−13 M to 10−5 M). (b) Linear relationships (R2 = 0.990): SERS intensity of the peak at 613 cm−1 corresponding to different R6G molecules concentrations. (c) The histogram and broken-line graph of SERS intensities of the peak at 613 cm−1 (R6G of 10−6 M) respectively collected from 10 random spots on one Au-Ag bi-metal NPs/MoS2 hybrid pyramidal SERS substrate and the above substrates of 10 batches.
Therefore, in this work, the SERS intensity (ISERS) of the peak at 613 cm−1 for R6G is ~94.91 as shown in Fig. 8(a), similarly, the normal Raman intensity (IRS) is ~98.12 according to our previous report [31]. And, CSERS (10−13 M) and CRS (10−3 M) are respectively the limit of detection (LOD) of analyte detected on the fabricated SERS substrate and on a clear SiO2 substrate. The EF can be easily calculated as (94.91/10−13 M)/(98.12/10−3 M) = 9.67 × 109. After demonstrating the excellent sensitivity and enhancement performance, the representative peaks at 613 cm−1 is chosen to study the quantitative detection by changing R6G concentration and recording the intensity of this band. Figure 8(b) shows a reasonable linear correlation between the intensity and R6G concentration. The linear equation is log(I) = 6.071 + 0.332 × log(C) (correlation coefficient: R2 = 0.990), where I and C is the relative SERS intensity of the peak and the R6G concentration, respectively. These results indicate that quantitative detection can be achieved based on this Au-Ag bi-metal NPs/MoS2 hybrid pyramidal SERS substrate. Noted that the error bar of intensity at every concentration is very little, which demonstrates the homogeneity of the obtained SERS signals. Furthermore, the sensitivity (The LOD is 10−12 M for CV) and the quantitative ability (R2: 0.983) of the SERS substrate was also verified in Fig. 9(a) and 9(b). To further evaluate the reproducibility of SERS substrate, the Raman detection of R6G molecules (10−6 M) was executed to respectively collect 10 spectra from 10 random spots on one Au-Ag bi-metal NPs/MoS2 hybrid pyramidal SERS substrate and the 10 batches SERS substrate. Therefore, as proved in Fig. 8(c), the histogram and broken-line graph of the SERS intensity of the peak at 613 cm−1 were collected to exhibit the slight fluctuation from spot to spot and from substrate to substrate. The maximum relative standard deviation (RSD) of these intensities can be calculated as follows [30]:
where the average intensity () and the fluctuating maximum intensity (I) among these collected relative intensity from spot to spot is ~12302.9 and ~13333, respectively. Thus, the RSD is ~8.37%. Similarly, for substrate to substrate, the RSD≈(|11415-12829.4|/12829.4) × 100%≈11.02%. Both the maximum RSD from spot to spot and from substrate to substrate are less than the standards (20%) for the reproducibility of an excellent SERS substrate [32], which verify the acceptable reproducibility of the well-designed Au-Ag bi-metal NPs/MoS2 hybrid pyramidal SERS substrate. These expected results can be ascribed to the following reasons. As we all know, the improvement of hot spot density will not only enhance the SERS signals of the probe molecules but also contribute to the optimal reproducibility of SERS substrate. Here, by tuning the edge-active sites of the MoS2 for the in situ fabrication of AuNPs by annealing the Ag film on the surface of the MoS2, the generation of Au-Ag bi-metal NPs serves the narrow nanogap and excites the dense hot spot under the stimulation of laser. And, the low-cost, simple and repeatable preparation technique will dedicate to the excellent reproducibility from substrate to substrate. Therefore, the high sensitivity and excellent reproducibility indicate that the Au-Ag bi-metal NPs/MoS2 hybrid pyramidal SERS substrate has great potential for practical applications.Fig. 9 (a) Investigating the Raman spectra of CV with the concentration from 10−12 to 10−7 M using the Au-Ag bi-metal NPs/MoS2 hybrid with pyramid SERS substrate. (b) The linear relation between Raman intensity of the CV fingerprint peak at 916 cm−1 and the various concentrations.
To study the practicability of the Au-Ag bi-metal NPs/MoS2 hybrid pyramidal SERS substrate applied in human food security, the melamine solution, which has been illegally abused to increase the content of nitrogen in milk products, especially, the infant formula. Human health is endangered when the levels of melamine in food products are over the minimum limit (0.15 mg/kg is approximately equal to 10−5 M in the USA and EU.). The melamine solution with the concentration from 10−3 to 10−10 M was obtained and added in Au-Ag bi-metal NPs/MoS2 hybrid pyramidal SERS substrate. The corresponding SERS spectra of the melamine solution are illustrated in Fig. 10(a). The characteristic peak at 1069 cm−1 is obviously recognized even for the molecules with the ultralow concentration (10−10 M). In addition, with increasing the concentration 10−10 M to 10−3 M, the relative SERS intensity is enhanced. As presented in Fig. 10(b), the relationship between the relative intensity and the different melamine concentration is described as the linear increasing with the equation [log(I) = 4.121 + 0.183 × log(C)] and the correlation coefficient (R2 = 0.977), which illustrates the quantitative ability of detecting melamine molecules. Therefore, the proposed Au-Ag bi-metal NPs/MoS2 hybrid pyramidal SERS substrate exhibits the great potential in detection of toxic molecules included in human food.
Fig. 10 (a) SERS spectra of melamine solution with different concentration. (b) The linear relationships of the peak (1069 cm−1) intensities as a function of the concentrations ranging from 10−3 to 10−10 M.
4. Conclusions
In conclusion, the Au-Ag bi-metal NPs/MoS2 hybrid pyramidal SERS substrate has been synthesized by introducing the edge-active sites of the MoS2 for the in situ fabrication of AuNPs by annealing the Ag film on the surface of the MoS2. Due to the generation of bimetal, the SERS performances including high EF, excellent sensitivity, quantitative ability, reproducibility and stability have been demonstrated in experiment and theory for both resonant and non-resonant molecules detection. Such a remarkable SERS sensor was further applied to sensitively detect the toxic melamine molecules and exhibits the great practical application potential in human food security.
Funding
National Natural Science Foundation of China (11504208, 11747072, 11774208, 11474187, 11674199, 11604040); Shandong Province Natural Science Foundation (ZR2017BA004, ZR2013HQ064, ZR2013AQ012, ZR2016AM19); A Project of Shandong Province Higher Educational Science and Technology Program (J18KZ011); China Postdoctoral Science Foundation (2016M602716).
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