Fabrication of micropatterned gold nanoparticles on graphene oxide nanosheet via thiol-Michael addition click chemistry

Fabrication of micropatterned gold nanoparticles on graphene oxide nanosheet via thiol-Michael addition click chemistry

Materials Letters xxx (xxxx) xxx Contents lists available at ScienceDirect Materials Letters journal homepage: www.elsevier.com/locate/mlblue Fabri...

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Materials Letters xxx (xxxx) xxx

Contents lists available at ScienceDirect

Materials Letters journal homepage: www.elsevier.com/locate/mlblue

Fabrication of micropatterned gold nanoparticles on graphene oxide nanosheet via thiol-Michael addition click chemistry Lei Nie a,b,⇑, Jingjing Zhang c, Qiaoyun Wu a, Guanghai Fei b, Kehui Hu b,d, Liang Fang e, Shoufeng Yang b a

College of Life Sciences, Xinyang Normal University, Xinyang 464000, China Department of Mechanical Engineering, Member of Flanders Make, KU Leuven (Catholic University of Leuven), Leuven 3001, Belgium c College of Physics and Electronic Engineering, Xinyang Normal University, Xinyang 464000, China d Department of Mechanical Engineering, Tsinghua University, Beijing 100084, China e Collaborative Innovative Center, Xinyang Normal University, Xinyang 464000, China b

a r t i c l e

i n f o

Article history: Received 10 August 2019 Received in revised form 30 October 2019 Accepted 12 November 2019 Available online xxxx Keywords: Carbon materials Nanoparticles Functional Click chemistry Structural

a b s t r a c t Here, the micropatterned gold nanoparticles (AuNPs) on graphene oxide (GO) nanosheet ([email protected]) was fabricated via thiol-Michael addition click reaction under ultraviolet (UV) light. First, AuNPs and GO were both functionalized by acrylamide and dithiothreitol, respectively, which were characterized by transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), dynamic light scattering (DLS) and ultraviolet–visible spectroscopy (UV–vis). The size of acrylamide modified AuNPs increased to 52.8 ± 16.5 nm compared to bare AuNPs (44.1 ± 14.5 nm). The [email protected] could be fabricated under the UV-light, and the UV–vis signal varied depending on the concentration of AuNPs. Also, the micropatterned structure of [email protected] nanosheet was accomplished by using a designed mask, which showed a high potential for cancer diagnosis and therapy. Ó 2019 Elsevier B.V. All rights reserved.

1. Introduction Graphene and graphene oxide (GO) has been emphasized with attention due to their chemical reduction and functionalization for diverse applications [1,2]. Particularly, GO has a 2D structure having sp3 carbon and unique oxygen-containing functional groups, such as epoxy, hydroxyl, and pairwise carboxyl groups [3–5]. Several ingenious methodologies were used to modify the p-conjugated planes of GO by anchoring micrometer and nanometer particles for biological sensors, energy, and photocatalysis applications [6–10]. Gold nanoparticles (AuNPs) have been essential in nano-scale technologies and devices [11,12]. The aqueous suspensions of AuNPs with high uniformity could be synthesized via several routes, such as the two-phase Brust-Schiffrin method and Turkevich method [13,14]. In recent years, AuNPs-GO nanocomposites have been applied in numerous fields; for instance, the glassy carbon electrode was modified by such nanocomposite for the detection of metal ions in seawater [5]. However, the AuNPs-GO nanocomposites were usually fabricated via chemical synthesis and electrostatic self-assembly with adding stabilizing agents ⇑ Corresponding author at: College of Life Sciences, Xinyang Normal University, Xinyang 464000, China. E-mail address: [email protected] (L. Nie).

[8,15,16]. It reported that AuNPs were attached to GO by the reduction of HAuCl4 using UV-light irradiation as reducing agent in aqueous media free of chemicals [17]. Besides, it was wellknown that the ‘‘click chemistry” showed quick, highly selective, and high yielding superiorities on connecting two components compared to other methods [18–21]. Here, we employed a ‘‘click chemistry” approach to achieve the conjunction between AuNPs and GO nanosheets. The AuNPs and GO nanosheets were functionalized by acrylamide and dithiothreitol molecules, respectively [22,23]. Then, the AuNPs were covalently bonded on GO nanosheets through thiol-Michael addition click reaction under UV-light, as shown in Scheme 1. The designed mask was used to fabricate the micropatterned [email protected] nanosheet via UV irradiation and further clean treatment. 2. Experimental 2.1. Materials Gold (III) chloride trihydrate (HAuCl43H2O, 49.0%) and Trisodium citrate dehydrate (SC, 98%) were purchased from SigmaAldrich. Tris(hydroxymethyl) aminomethane (TB, GR), 2-hydroxy40 -(2-hydroxyethoxy)-2-methylpropiophenone (I-2959, 98%) and Acrylamide (GR) were obtained from Macklin. All chemicals were used as received without further purification.

https://doi.org/10.1016/j.matlet.2019.127014 0167-577X/Ó 2019 Elsevier B.V. All rights reserved.

Please cite this article as: L. Nie, J. Zhang, Q. Wu et al., Fabrication of micropatterned gold nanoparticles on graphene oxide nanosheet via thiol-Michael addition click chemistry, Materials Letters, https://doi.org/10.1016/j.matlet.2019.127014

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Scheme 1. A schematic illustration of [email protected] nanosheets fabricated via thiol-Michael addition click chemistry and manufactured the micropatterned [email protected] nanosheet as well.

2.2. Synthesis of acrylamide modified AuNPs

2.3. Synthesis of dithiothreitol modified GO (dtt-GO) nanosheets

First, AuNPs were prepared (Supplementary Materials) [22]. The pre-synthesized AuNPs solution (15 mL) was centrifuged at 4500g for 10 min (Allegra X-30R Centrifuge). The supernatant was poured out, and the residue was re-dispersed in Millipore water (15 mL). Then, 1 mL acrylamide (7 lg/mL in water) and 1 mL I-2959 (70 ng/mL in water) were added and stirred for 12 h.

An improved Hummers method was used to prepare the GO nanosheets (Supplementary Materials) [24]. 4 mL brownish GO solution (0.01 g/mL) was added into a flask, then, dithiothreitol (2.58 mM) was added with constant stirring at 90 °C, and 30 min later, homogeneous dtt-GO nanosheets were obtained, which was stored at room temperature.

Fig. 1. TEM images of (a) bare AuNPs and (b) acrylamide-AuNPs; (c) UV–vis spectra of bare AuNPs and acrylamide-AuNPs; (d) XPS spectra of acrylamide-AuNPs, and XPS spectrum of (e) C1s, (f) O1s, (g) N1s, and (h) Au4f confirmed the successful synthesis of acrylamide-AuNPs.

Please cite this article as: L. Nie, J. Zhang, Q. Wu et al., Fabrication of micropatterned gold nanoparticles on graphene oxide nanosheet via thiol-Michael addition click chemistry, Materials Letters, https://doi.org/10.1016/j.matlet.2019.127014

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2.4. Fabrication of [email protected] nanosheets First, the prepared acrylamide-AuNPs solution and dtt-GO nanosheets solution was sonicated for 1 h. 2 mL of acrylamideAuNPs solution and 1 mL of dtt-GO nanosheets solution were mixed homogeneously, then, a drop of mixed solution was dropped on a cover glass, and spread out evenly, after later, under UV-light for 10 min. The designation of [email protected] S1, [email protected] S2, [email protected] S3 represent using 1 mL, 200 lL, and 100 lL of dttGO nanosheets solution, respectively. The micropatterned

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[email protected] nanosheets were fabricated via a designed mask used under UV-light (Supplementary Materials). 2.5. Characterization The prepared acrylamide-AuNPs were characterized by Transmission Electron Microscope (TEM, Tecnai G2 F20), X-ray Photoelectron Spectroscopy (XPS, K-alpha 0.05 eV, Thermo Scientific), Dynamic Light Scattering (DLS, Mastersizer 3000E) and Ultraviolet–visible spectroscopy (UV–vis, PerkinElmer Lambda 950). The

Fig. 2. TEM image of (a) dtt-GO nanosheets; (b) XPS spectra of dtt-GO nanosheets, and XPS spectrum of (c) C1s, (d) O1s, and (e) S2p identified that the covalently bond between dithiothreitol and GO nanosheets.

Fig. 3. TEM images of (a) [email protected] nanosheets, the insets at top and bottom were enlarged at a higher magnifications from edge and interior area respectively; (b) UV–vis spectra of [email protected] nanosheets fabricated by using different concentration of GO nanosheets; (c) a schematic illustration of micropatterned [email protected] nanosheets via UVlight exposure and clean treatments, AuNPs were not detected at (d) unreacted areas (TEM image), however, AuNPs were observed at (e) reacted areas (TEM image).

Please cite this article as: L. Nie, J. Zhang, Q. Wu et al., Fabrication of micropatterned gold nanoparticles on graphene oxide nanosheet via thiol-Michael addition click chemistry, Materials Letters, https://doi.org/10.1016/j.matlet.2019.127014

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L. Nie et al. / Materials Letters xxx (xxxx) xxx

dtt-GO nanosheets and [email protected] nanosheets were characterized by using TEM, XPS, and UV–vis. 3. Results and discussion The ‘‘click chemistry” has drawn a great deal of attention in organic synthesis, polymer functionalization, and nanocomposite surface modification [25]. The well-known thiol-Michael addition click reaction involved the hydrothiolation of an alkene, which initiated thermally or photochemically with or without adding photoinitiator [26,27]. Herein, the AuNPs were attached on the surface of GO nanosheet via thiol-Michael addition click reaction under UV-light (Scheme 1). Fig. 1 showed the properties of acrylamide-AuNPs. Compared to bare AuNPs (44.1 ± 14.5 nm), the size of prepared acrylamide-AuNPs increased (52.8 ± 16.5 nm). The UV–vis retention spectra of bare AuNPs and acrylamideAuNPs were shown in Fig. 1c, the presence of the band at ca. 520 nm was mainly due to surface plasmon reverberation of AuNPs, and the aggregation of acrylamide-AuNPs resulted in slight red shift of surface plasmon resonance (SPR) peak (Fig. S1) [28–30]. The acrylamide on the surface of AuNPs gave rise to the slight clustering of AuNPs (Fig. S2), and the zeta potential validated the excellent stability of acrylamide-AuNPs (Fig. S3). The XPS spectrum of acrylamide-AuNPs showed C1s, O1s, N1s, and Au4f peaks, indicating the connection between AuNPs and acrylamide (Fig. 1d–h). The binding energy of acrylamide-AuNPs was red-shifted by 0.4 eV compared with the bare AuNPs, which due to the effect of cluster size on binding energy (Fig. S4) [31]. On the other hand, the morphology of dtt-GO nanosheets was examined by TEM (Fig. 2a). The prepared dtt-GO nanosheets presented a transparent multi-layer structure with folds. Compared to bare GO nanosheets (Fig. S5), the thickness of dtt-GO nanosheets has increased, speculating that more layers stacked together. XPS measurements were performed to further understand the thiol groups on GO nanosheets (Fig. 2b). The C1s, O1s, and S2p scanning spectra proved the formation of C–S bonds on the surface of GO nanosheets. The AuNPs were distributed and decorated on the surface of GO nanosheets via UV-light exposure, which was characterized using TEM and UV–vis (Fig. 3). The AuNPs were observed on the GO surface, the presence of intensive AuNPs was readily viewed at the border, and distinctive regions of GO nanosheets (insets of Fig. 3a). However, few AuNPs were detected on unmodified GO nanosheets (Fig. S6). The UV–vis absorption of spectra for [email protected] nanosheets showed two peaks at about 340.0 and 520.0 nm, which corresponded to the plasmon resonance of dttGO and acrylamide-AuNPs, indicating the successful bonding of AuNPs on GO nanosheets [32]. Also, the intensity of SPR peak at ca. 520 nm was regulated by using different dosage of dtt-GO nanosheets. Lastly, the micropatterned [email protected] nanosheets were further fabricated using a designed mask during UV-light exposure (Fig. 3c–e). Gold has a remarkable capacity to absorb and scatter light over the visible region, which depending on the particles’ size, shape, and array, thus the obtained micropatterned [email protected] nanosheets could be applied for biomedical imaging, biosensors, cancer diagnosis, and therapy applications [8,33]. 4. Conclusion In summary, the acrylamide modified AuNPs and dithiothreitol functionalized GO nanosheets were successfully synthesized. The AuNPs were covalently scheduled on the surface of GO nanosheets via thiol-Michael addition click reaction, confirmed via TEM and UV–vis analysis. The intensity of SPR peak for [email protected] nanosheets at around 520 nm varied on using different dosage of dtt-GO nanosheets. Last, the micropatterned [email protected]

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Please cite this article as: L. Nie, J. Zhang, Q. Wu et al., Fabrication of micropatterned gold nanoparticles on graphene oxide nanosheet via thiol-Michael addition click chemistry, Materials Letters, https://doi.org/10.1016/j.matlet.2019.127014