Name: 著者スポットライト:合成AgNPを用いたSERSフレキシブル基板の開発と応用
Uploaded: 2023-11-17T14:00:00
Description: Watch this Scientific Journal Video about Development and Application of SERS Flexible Substrates Using Synthesized AgNPs at JoVE.com

この研究は、中国国家自然科学基金会(助成金番号61974004および61931018)および中国国家重点研究開発プログラム(助成金番号2021YFB3200100)の支援を受けています。この研究は、北京大学の電子顕微鏡研究所が電子顕微鏡へのアクセスを提供したことを認めています。さらに、この研究は、ラマン測定の支援をしてくれたYing Cui氏と北京大学地球宇宙科学院にも感謝しています。

1. ナノ粒子の合成
<ol><li>硝酸銀溶液の調製<ol><li>精密天秤を使用して、0.0017 g の AR グレード硝酸銀(AgNO3、 材料表を参照)を測定し、10 mL の脱イオン(DI)水に加えます。混合物を撹拌して、10-3 mol/L AgNO3 溶液を作成します。</li>
	</ol></li>
	<li>銀 - アンモニア錯体の調製<ol><li>ARグレードのアンモニア水1mL(NH3.H2O、 材料表</strong...

R6GおよびThiramのSERS検出用フレキシブル基板の作製

<ol>
	<li>Zheng, F., Ke, W., Shi, L., Liu, H., Zhao, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Plasmonic+Au-Ag+janus+nanoparticle+engineered+ratiometric+surface-enhanced+Raman+scattering+aptasensor+for+ochratoxin+A+detection.">Plasmonic Au-Ag janus nanoparticle engineered ratiometric surface-enhanced Raman scattering aptasensor for ochratoxin A detection.</a> Analytical Chemistry. 91 (18), 11812-11820 (2019).</li><li>Zhou, L., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Size-tunable+gold+aerogels:+a+durable+and+misfocus-tolerant+3D+substrate+for+multiplex+SERS+detection.">Size-tunable gold aerogels: a durable and misfocus-tolerant 3D substrate for multiplex SERS detection.</a> Advanced Optical Materials. 9 (17), 2100352 (2021).</li><li>Fan, W., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Graphene+oxide+and+shape-controlled+silver+nanoparticle+hybrids+for+ultrasensitive+single-particle+surface-enhanced+Raman+scattering+(SERS)+sensing.">Graphene oxide and shape-controlled silver nanoparticle hybrids for ultrasensitive single-particle surface-enhanced Raman scattering (SERS) sensing.</a> Nanoscale. 6 (9), 4843-4851 (2014).</li><li>Xu, W., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Graphene-veiled+gold+substrate+for+surface-enhanced+Raman+spectroscopy.">Graphene-veiled gold substrate for surface-enhanced Raman spectroscopy.</a> Advanced Materials. 25 (6), 928-933 (2013).</li><li>Li, H., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Graphene-coated+Si+nanowires+as+substrates+for+surface-enhanced+Raman+scattering.">Graphene-coated Si nanowires as substrates for surface-enhanced Raman scattering.</a> Applied Surface Science. 541, 0169-4332 (2021).</li><li>Chin, C. Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=High+sensitivity+enhancement+of+multi-shaped+silver-nanoparticle-decorated+hydrophilic+PVDF-based+SERS+substrates+using+solvating+pretreatment.">High sensitivity enhancement of multi-shaped silver-nanoparticle-decorated hydrophilic PVDF-based SERS substrates using solvating pretreatment.</a> Sensors and Actuators: B. Chemistry. 347, 130614 (2021).</li><li>Volpe, G., Noack, M., Acimovic, S. S., Reinhardt, C., Quidant, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Near-field+mapping+of+plasmonic+antennas+by+multiphoton+absorption+in+poly(methyl+methacrylate).">Near-field mapping of plasmonic antennas by multiphoton absorption in poly(methyl methacrylate).</a> Nano Letters. 12 (9), 4864-4868 (2012).</li><li>Novikov, S. M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Fractal+shaped+periodic+metal+nanostructures+atop+dielectric-metal+substrates+for+SERS+applications.">Fractal shaped periodic metal nanostructures atop dielectric-metal substrates for SERS applications.</a> ACS Photonics. 7 (7), 1708-1715 (2020).</li><li>Li, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=300+mm+wafer-level,+ultra-dense+arrays+of+Au-capped+nanopillars+with+sub-10+nm+gaps+as+reliable+SERS+substrates.">300 mm wafer-level, ultra-dense arrays of Au-capped nanopillars with sub-10 nm gaps as reliable SERS substrates.</a> Nanoscale. 6 (21), 12391-12396 (2014).</li><li>Mecker, L. C., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Selective+melamine+detection+in+multiple+sample+matrices+with+a+portable+Raman+instrument+using+surface-enhanced+Raman+spectroscopy-active+gold+nanoparticles.">Selective melamine detection in multiple sample matrices with a portable Raman instrument using surface-enhanced Raman spectroscopy-active gold nanoparticles.</a> Analytica Chimica Acta. 733, 48-55 (2012).</li><li>Shao, J. D., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=PLLA+nanofibrous+paper-based+plasmonic+substrate+with+tailored+hydrophilicity+for+focusing+SERS+detection.">PLLA nanofibrous paper-based plasmonic substrate with tailored hydrophilicity for focusing SERS detection.</a> ACS Applied Materials &amp; Interfaces. 7, 5391-5399 (2015).</li><li>Chen, Y. M., Ge, F. Y., Guang, S. Y., Cai, Z. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Low-cost+and+large-scale+flexible+SERS-cotton+fabric+as+a+wipe+substrate+for+surface+trace+analysis.">Low-cost and large-scale flexible SERS-cotton fabric as a wipe substrate for surface trace analysis.</a> Applied Surface Science. 436, 111-116 (2018).</li><li>Yang, L., Zhen, S. J., Li, Y. F., Huang, C. Z. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Silver+nanoparticles+deposited+on+graphene+oxide+for+ultrasensitive+surface-enhanced+Raman+scattering+immunoassay+of+cancer+biomarker.">Silver nanoparticles deposited on graphene oxide for ultrasensitive surface-enhanced Raman scattering immunoassay of cancer biomarker.</a> Nanoscale. 10, 11942-11947 (2018).</li><li>Creedon, N. C., Lovera, P., Furey, A., O'Riordan, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Transparent+polymer-based+SERS+substrates+templated+by+a+soda+can.">Transparent polymer-based SERS substrates templated by a soda can.</a> Sensors and Actuators, B. 259, 64-74 (2018).</li><li>Shiohara, A., Langer, J., Polavarapu, L., Marzan, L. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Solution+processed+polydimethylsiloxane/gold+nanostar+flexible+substrates+for+plasmonic+sensing.">Solution processed polydimethylsiloxane/gold nanostar flexible substrates for plasmonic sensing.</a> Nanoscale. 6, 9817-9823 (2014).</li><li>Guo, H. Y., Jiang, D., Li, H. B., Xu, S. P., Xu, W. Q. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Highly+efficient+construction+of+silver+nanosphere+dimers+on+poly+(dimethylsiloxane)+sheets+for+surface-enhanced+Raman+scattering.">Highly efficient construction of silver nanosphere dimers on poly (dimethylsiloxane) sheets for surface-enhanced Raman scattering.</a> Journal of Physical Chemistry C. 117, 564-570 (2013).</li><li>Park, S., Lee, J., Ku, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Transparent+and+flexible+surface-enhanced+Raman+scattering+(SERS)+sensors+based+on+gold+nanostar+arrays+embedded+in+silicon+rubber+film.">Transparent and flexible surface-enhanced Raman scattering (SERS) sensors based on gold nanostar arrays embedded in silicon rubber film.</a> ACS Applied Materials Interfaces. 9, 44088-44095 (2017).</li><li>Li, L. M., Chin, W. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Rapid+fabrication+of+a+flexible+and+transparent+Ag+nanocubes@+PDMS+film+as+a+SERS+substrate+with+high+performance.">Rapid fabrication of a flexible and transparent Ag nanocubes@ PDMS film as a SERS substrate with high performance.</a> ACS Applied Materials &amp; Interfaces. 12 (33), 37538-37548 (2020).</li><li>Yang, J. L., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Quantitative+detection+using+two-dimensional+shell-isolated+nanoparticle+film.">Quantitative detection using two-dimensional shell-isolated nanoparticle film.</a> Journal of Raman Spectroscopy. 48, 919-924 (2017).</li><li>Fortuni, B., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=In+situ+synthesis+of+Au-shelled+Ag+nanoparticles+on+PDMS+for+flexible,+long-life,+and+broad+spectrum-sensitive+SERS+substrates.">In situ synthesis of Au-shelled Ag nanoparticles on PDMS for flexible, long-life, and broad spectrum-sensitive SERS substrates.</a> Chemical Communications. 53 (82), 11298-11301 (2017).</li><li>Wu, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Graphene+oxide+scroll+meshes+prepared+by+molecular+combing+for+transparent+and+flexible+electrodes.">Graphene oxide scroll meshes prepared by molecular combing for transparent and flexible electrodes.</a> Advanced Materials Technologies. 2 (2), 1600231 (2017).</li><li>Li, Z. Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Silver+nanowire-templated+molecular+nanopatterning+and+nanoparticle+assembly+for+surface-enhanced+Raman+scattering.">Silver nanowire-templated molecular nanopatterning and nanoparticle assembly for surface-enhanced Raman scattering.</a> Chemistry-A European Journal. 25 (45), 10561-10565 (2019).</li><li>Zhan, H. R., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Transfer+printing+for+preparing+nanostructured+PDMS+film+as+flexible+SERS+active+substrate.">Transfer printing for preparing nanostructured PDMS film as flexible SERS active substrate.</a> Composites Part B: Engineering. 84, 222-227 (2016).</li><li>West, P., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Searching+for+better+plasmonic+materials.">Searching for better plasmonic materials.</a> Laser &amp; Photonics Reviews. 4, 795-808 (2010).</li><li>Anastassiades, M., Lehotay, S. J., &#352;tajnbaher, d., Schenck, F. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Fast+and+easy+multiresidue+method+employing+acetonitrile+extraction/partitioning+and+&amp;#34;dispersive+solid-phase+extraction&amp;#34;+for+the+determination+of+pesticide+residues+in+produce.">Fast and easy multiresidue method employing acetonitrile extraction/partitioning and &amp;#34;dispersive solid-phase extraction&amp;#34; for the determination of pesticide residues in produce.</a> Journal of AOAC International. 86 (2), 412-431 (2003).</li><li>Zhu, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+green+chemistry+synthesis+of+Ag+nanoparticles+and+their+concentrated+distribution+on+PDMS+elastomer+film+for+more+sensitive+SERS+detection.">A green chemistry synthesis of Ag nanoparticles and their concentrated distribution on PDMS elastomer film for more sensitive SERS detection.</a> , (2017).</li><li>Damalas, C. A., Eleftherohorinos, I. G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Pesticide+exposure,+safety+issues,+and+risk+assessment+indicators.">Pesticide exposure, safety issues, and risk assessment indicators.</a> International Journal of Environmental Research and Public Health. 8 (5), 1402-1419 (2011).</li><li>Zannotti, M., Rossi, A., Giovannetti, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=SERS+activity+of+silver+nanosphere,+triangular+nanoplates,+hexagonal+nanoplates+and+quasi-spherical+nanoparticles:+effect+of+shape+and+morphology.">SERS activity of silver nanosphere, triangular nanoplates, hexagonal nanoplates and quasi-spherical nanoparticles: effect of shape and morphology.</a> Coatings. 10, 288 (2020).</li><li>Zhu, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Large-scale+fabrication+of+ultrasensitive+and+uniform+surface-enhanced+Raman+scattering+substrates+for+the+trace+detection+of+pesticides.">Large-scale fabrication of ultrasensitive and uniform surface-enhanced Raman scattering substrates for the trace detection of pesticides.</a> Nanomaterials. 8 (7), 520 (2018).</li><li>Lu, H., Zhu, L., Zhang, C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mixing+assisted+&amp;#34;hot+spots&amp;#34;+occupying+SERS+strategy+for+highly+sensitive+in+situ+study.">Mixing assisted &amp;#34;hot spots&amp;#34; occupying SERS strategy for highly sensitive in situ study.</a> Analytical Chemistry. 90 (7), 4535-4543 (2018).</li><li>Mao, H., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Microfluidic+surface-enhanced+Raman+scattering+sensors+based+on+nanopillar+forests+realized+by+an+oxygen-plasma-stripping-of-photoresist+technique.">Microfluidic surface-enhanced Raman scattering sensors based on nanopillar forests realized by an oxygen-plasma-stripping-of-photoresist technique.</a> Small. 10 (1), 127-134 (2014).</li><li>Zhang, C. H., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Small+and+sharp+triangular+silver+nanoplates+synthesized+utilizing+tiny+triangular+nuclei+and+their+excellent+SERS+activity+for+selective+detection+of+Thiram+residue+in+soil.">Small and sharp triangular silver nanoplates synthesized utilizing tiny triangular nuclei and their excellent SERS activity for selective detection of Thiram residue in soil.</a> ACS Applied Materials and Interfaces. 9, 17387-17398 (2017).</li><li>Zhu, C., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Detection+of+dithiocarbamate+pesticides+with+a+spongelike+surface-enhanced+raman+scattering+substrate+made+of+reduced+graphene+oxide-wrapped+silver+nanocubes.">Detection of dithiocarbamate pesticides with a spongelike surface-enhanced raman scattering substrate made of reduced graphene oxide-wrapped silver nanocubes.</a> ACS Applied Materials and Interfaces. 9, 39618-39625 (2017).</li><li>Zhu, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Highly+sensitive+and+label-free+determination+of+thiram+residue+using+surface-enhanced+Raman+spectroscopy+(SERS)+coupled+with+paper-based+microfluidics.">Highly sensitive and label-free determination of thiram residue using surface-enhanced Raman spectroscopy (SERS) coupled with paper-based microfluidics.</a> Analytical Methods. 9, 6186-6193 (2017).</li><li>Yu, Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Gold-nanorod-coated+capillaries+for+the+SERS-based+detection+of+Thiram.">Gold-nanorod-coated capillaries for the SERS-based detection of Thiram.</a> ACS Applied Nano Materials. 2 (1), 598-606 (2019).</li><li>Zhang, X., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Rapid+and+non-invasive+surface-enhanced+Raman+spectroscopy+(SERS)+detection+of+chlorpyrifos+in+fruits+using+disposable+paper-based+substrates+charged+with+gold+nanoparticle/halloysite+nanotube+composites.">Rapid and non-invasive surface-enhanced Raman spectroscopy (SERS) detection of chlorpyrifos in fruits using disposable paper-based substrates charged with gold nanoparticle/halloysite nanotube composites.</a> Mikrochim Acta. 189, 189-197 (2022).</li><li>Lee, C. H., Tian, L., Singamaneni, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Paper-based+SERS+swab+for+rapid+trace+detection+on+real-world+surfaces.">Paper-based SERS swab for rapid trace detection on real-world surfaces.</a> ACS Applied Materials and Interfaces. 2, 3429-3435 (2010).</li><li>Cheng, H., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Drug+preconcentration+and+direct+quantification+in+biofluids+using+3D-printed+paper+cartridge.">Drug preconcentration and direct quantification in biofluids using 3D-printed paper cartridge.</a> Biosensors and Bioelectronics. 189, 113266-113277 (2021).</li></ol>

本研究では、化学修飾によりAgNPとPDMSを結合させたフレキシブルSERS基板を導入し、優れた性能を達成しました。粒子合成中、特に銀アンモニア錯体合成(ステップ1.2)では、溶液の色が重要な役割を果たします。水滴にアンモニアを添加しすぎると、AgNPの合成品質に悪影響を及ぼし、検出結果に失敗する可能性があります。合成プロセス中の基質修飾(ステップ2.2)に注意を払う必要があります?...

表面増強ラマン散乱(SERS)は、ラマン散乱の一種として、高感度で穏やかな検出条件という利点があり、単一分子検出も実現できます1,2,3,4。金や銀などの金属ナノ構造は、通常、物質検出を可能にするためのSERS基板として使用されます5,6。ナノ構造表面の電磁結合強化は、SERSアプリケーションにおいて重要な役割を果たします。さまざまなサイズ、形状、粒子間距離、組成の金属ナノ構造が凝集して多数の「ホットスポット」を形成し、局所的な表面プラズモン共鳴により強い電磁場を生成する可能性があります7,8。多くの研究により、SERS基質として異なる形態の金属ナノ粒子が開発され、SERS増強の達成における有効性が実証されています9,10。
フレキシブルSERS基板は、SERS効果を生み出すことができるナノ構造をフレキシブル基板上に堆積させ、曲面での直接検出を容易にすることで、幅広い用途に使用されています。フレキシブルSERS基質は、不規則な表面、非平面的な表面、または曲面上の分析種の検出と収集に使用されます。一般的なフレキシブルSERS基板には、繊維、ポリマーフィルム、および酸化グラフェンフィルムが含まれる11,12,13,14。その中で、ポリジメチルシロキサン(PDMS)は最も広く使用されているポリマー材料の1つであり、高い透明性、高い引張強度、化学的安定性、非毒性、接着性などの利点があります15,16,17。PDMSはラマン断面積が小さいため、ラマン信号への影響はごくわずかです18。PDMSプレポリマーは液状であるため、熱や光で硬化させることができ、高い制御性と利便性を提供します。PDMSベースのSERS基質は、比較的一般的なフレキシブルSERS基質であり、例示的な性能を有する異なる生化学物質を検出するための様々な金属ナノ粒子を埋め込むために以前の研究で使用されてきた19,20。
SERS基板の作製では、ナノギャップ構造の作製が重要です。物理堆積技術には、高いスケーラビリティ、均一性、再現性などの利点がありますが、通常、良好な真空条件と特殊な機器が必要であり、その実用化には限界があります21。さらに、数ナノメートルスケールでナノ構造を作製することは、従来の堆積技術では依然として困難である22。その結果、化学的手法で合成されたナノ粒子は、様々な相互作用により柔軟な透明膜に吸着し、ナノスケールでの金属構造の自己組織化を促進することができます。吸着の成功を確実にするために、フィルム表面を物理的または化学的に修飾してその表面親水性を変化させることによって相互作用を調整することができる23。銀ナノ粒子は、金ナノ粒子と比較して、より優れたSERS性能を示すが、その不安定性、特に空気中での酸化に対する感受性は、SERS増強係数(EF)の急速な低下をもたらし、基板性能に影響を与える24。そのため、安定な粒子法の開発が不可欠です。
残留農薬の存在は大きな注目を集めており、現場で食品中のさまざまなクラスの有害化学物質を迅速に検出および特定できる堅牢な方法が緊急に必要とされています25,26。フレキシブルSERS基板は、実用化、特に食品安全の分野で独自の利点を提供します。本稿では、合成したグルコース被覆銀ナノ粒子(AgNP)をPDMS基板上に結合させることにより、フレキシブルSERS基板を調製する方法を紹介します(図1)。グルコースの存在はAgNPを保護し、空気中の銀の酸化を軽減します。この基質は優れた検出性能を発揮し、ローダミン6G(R6G)を10〜10M、農薬チラムを10〜8Mと低く検出し、均一性に優れています。さらに、フレキシブル基板は、ボンディングやサンプリングによる検出にも使用でき、多くのアプリケーションシナリオが考えられます。

<table border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always">
	<tbody>
		<tr>
			<td>Ammonia (NH3.H2O, 25%)</td>
			<td>Beijing Chemical Works</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>APTES (98%)</td>
			<td>Beyotime</td>
			<td>ST1087</td>
			<td></td>
		</tr>
		<tr>
			<td>BD-20AC Laboratory Chrona Treater</td>
			<td>Electro-Technic Products Inc.</td>
			<td>12051A</td>
			<td></td>
		</tr>
		<tr>
			<td>D-glucose</td>
			<td>Beijing Chemical Works</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Environmental Scanning electron microscope (ESEM)</td>
			<td>FEI</td>
			<td>QUANTA 250</td>
			<td></td>
		</tr>
		<tr>
			<td>Raman microscope</td>
			<td>Horiba JY</td>
			<td>LabRAM HR Evolution</td>
			<td></td>
		</tr>
		<tr>
			<td>Rhodamine 6G</td>
			<td>Beijing Chemical Works</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Silicone Elastomer Base and Silicone Elastomer Curing Agent</td>
			<td>Dow Corning Corporation</td>
			<td>SYLGARD 184</td>
			<td></td>
		</tr>
		<tr>
			<td>Silver nitrate</td>
			<td>Beijing Chemical Works</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Thiram (C6H12N2S2, 99.9%)</td>
			<td>Beijing Chemical Works</td>
			<td></td>
			<td></td>
		</tr>
	</tbody>
</table>

fabrication of polydimethylsiloxane (pdms)-based flexible surface-enhanced raman scattering (sers) substrate for ultrasensitive detection

本稿では、表面増強ラマン散乱(SERS)用に設計されたフレキシブル基板の作製方法を紹介します。銀ナノ粒子(AgNP)は、硝酸銀(AgNO3)とアンモニアとの錯体化反応を経て合成され、その後グルコースで還元されました。得られたAgNPは、20nmから50nmの範囲で均一な粒度分布を示しました。続いて、3-アミノプロピルトリエトキシシラン(APTES)を用いて、酸素プラズマで表面処理したPDMS基板を改質しました。このプロセスにより、基板上へのAgNPの自己組織化が容易になりました。様々な実験条件が基板性能に及ぼす影響を系統的に評価した結果、優れた性能とエンハンスドファクター(EF)を持つSERS基板が開発されました。この基質を利用して、R6G(ローダミン6G)で10-10 M、チラムで10-8 Mという優れた検出限界を達成しました。この基質は、リンゴの残留農薬の検出に使用され、非常に満足のいく結果が得られました。フレキシブルなSERS基板は、複雑なシナリオでの検出など、実際のアプリケーションに大きな可能性を秘めています。

Surface-Enhanced Raman Scattering (SERS), as a type of Raman scattering, offers the advantages of high sensitivity and gentle detection conditions, and can even achieve single molecule detection1,2,3,4. Metal nanostructures, such as gold and silver, are typically used as SERS substrates to enable substance detection5,6. Electromagnetic coupling enhancement on nanostructured surfaces plays a significant role in SERS applications. Metallic nanostructures with varying sizes, shapes, interparticle distances, and compositions can aggregate to create numerous &#34;hotspots&#34; generating intense electromagnetic fields due to localized surface plasmon resonances7,8. Many studies have developed metal nanoparticles with different morphologies as SERS substrates, demonstrating their effectiveness in achieving SERS enhancement9,10.
Flexible SERS substrates find wide applications, with nanostructures capable of producing SERS effects deposited on flexible substrates to facilitate direct detection on curved surfaces. Flexible SERS substrates are employed for detecting and collecting analytes on irregular, non-planar, or curved surfaces. Common flexible SERS substrates include fibers, polymer films, and graphene oxide films11,12,13,14. Among them, polydimethylsiloxane (PDMS) is one of the most widely used polymer materials and offers advantages such as high transparency, high tensile strength, chemical stability, non-toxicity, and adhesion15,16,17. PDMS has a low Raman cross-section, making its impact on the Raman signal negligible18. Since the PDMS prepolymer is in liquid form, it can be cured by heat or light, providing a high degree of controllability and convenience. PDMS-based SERS substrates are relatively common flexible SERS substrates, having been used in previous studies to embed various metal nanoparticles for detecting different biochemical substances with exemplary performance19,20.
In the preparation of SERS substrates, the fabrication of nanogap structures is crucial. Physical deposition technology offers advantages like high scalability, uniformity, and reproducibility but typically requires good vacuum conditions and specialized equipment, limiting its practical applications21. Additionally, fabricating nanostructures at the few-nanometer scale remains challenging with conventional deposition techniques22. Consequently, nanoparticles synthesized through chemical methods can be adsorbed onto flexible transparent films through various interactions, facilitating the self-assembly of metallic structures at the nanoscale. To ensure successful adsorption, interactions can be adjusted by physically or chemically modifying the film surface to alter its surface hydrophilicity23. Silver nanoparticles, compared to gold nanoparticles, exhibit better SERS performance, but their instability, particularly their susceptibility to oxidation in air, results in a rapid decrease in the SERS Enhancement Factor (EF), affecting substrate performance24. Hence, it is essential to develop a stable particle method.
The presence of pesticide residues has garnered significant attention, creating a pressing need for robust methods capable of rapidly detecting and identifying various classes of hazardous chemicals in food in the field25,26. Flexible SERS substrates offer unique advantages in practical applications, particularly in the realm of food safety. This article introduces a method for preparing a flexible SERS substrate by bonding synthesized glucose-coated silver nanoparticles (AgNPs) onto a PDMS substrate (Figure 1). The presence of glucose protects the AgNPs, mitigating silver oxidation in the air. The substrate demonstrates excellent detection performance, capable of detecting Rhodamine 6G (R6G) as low as 10-10 M and pesticide Thiram as low as 10-8 M, with good uniformity. Moreover, the flexible substrate can be employed for detection through bonding and sampling, with numerous potential application scenarios.

著者スポットライト:合成AgNPを用いたSERSフレキシブル基板の開発と応用 

超高感度検出のためのポリジメチルシロキサン(PDMS)ベースのフレキシブル表面増強ラマン散乱(SERS)基板の作製

This protocol describes preparing SERS flexible substrates, applying them to actual detection scenarios. The SERS flexible substrate offered by this protocol is environmental friendly and achieves good detection performance. The silver nanoparticles can be synthesized easily by simple vessels, and do not require complicated experimental conditions and environment.In our laboratory, we plan to focus on researching the silver nanoparticles synthesized through the vessel used in this study. We'll explore methods to enhance their SERS detection capabilities, and leverage their unique properties and characteristics to design better performing SERS detection substrates.

本研究では、合成AgNPをグルコースで包み、APTESを用いてPDMS上で自己組織化させた柔軟なSERS基質を開発し、実用的な農薬検出アプリケーションにおいて優れた検出性能を実現しました。R6G と Thiram の検出限界は、それぞれ 10-10 M と 10-8 M で到達し、エンハンスメント係数 (EF) は 1 x 10 5 でした。さらに、基板は均一性を示した。
グルコースに包まれ...

Watch this Scientific Journal Video about Development and Application of SERS Flexible Substrates Using Synthesized AgNPs at JoVE.com

このプロトコルでは、表面増強ラマン散乱用のフレキシブル基板の製造方法について説明します。この分析法は、低濃度の R6G と Thiram の検出に使用されています。

This article presents a fabrication method for a flexible substrate designed for Surface-Enhanced Raman Scattering (SERS). Silver nanoparticles (AgNPs) ...

このプロトコルでは、SERSフレキシブル基板を調製し、実際の検出シナリオに適用する方法について説明します。このプロトコルが提供するSERSフレキシブル基板は、環境に優しく、優れた検出性能を実現します。銀ナノ粒子は、単純な容器で容易に合成でき、複雑な実験条件や環境を必要としません。当研究室では、本研究で用いた容器を通して合成された銀ナノ粒子の研究に注力していく予定です。SERS検出機能を強化し、その独自の特性と特性を活用して、より高性能なSERS検出基板を設計する方法を探ります。

fabrication-polydimethylsiloxane-pdms-based-flexible-surface-enhanced

Research

JoVE Journal

Engineering

Fabrication of polydimethylsiloxane (PDMS)-Based Flexible Surface-Enhanced Raman Scattering (SERS) Substrate for Ultrasensitive Detection

This article presents a fabrication method for a flexible substrate designed for Surface-Enhanced Raman Scattering (SERS). Silver nanoparticles (AgNPs) were synthesized through a complexation reaction involving silver nitrate (AgNO3) and ammonia, followed by reduction using glucose. The resulting AgNPs exhibited a uniform size distribution ranging from 20 nm to 50 nm. Subsequently, 3-aminopropyl triethoxysilane (APTES) was employed to modify a PDMS substrate that had been surface-treated with oxygen plasma. This process facilitated the self-assembly of AgNPs onto the substrate. A systematic evaluation of the impact of various experimental conditions on substrate performance led to the development of a SERS substrate with excellent performance and an Enhanced Factor (EF). Utilizing this substrate, impressive detection limits of 10-10 M for R6G (Rhodamine 6G) and 10-8 M for Thiram were achieved. The substrate was successfully employed for detecting pesticide residues on apples, yielding highly satisfactory results. The flexible SERS substrate demonstrates great potential for real-world applications, including detection in complex scenarios.

This protocol describes a fabrication method for a flexible substrate for surface-enhanced Raman scattering. This method has been used in the successful detection of low concentrations of R6G and Thiram.

工学

Synthesis of Silver Nanoparticles and Preparation of Flexible SERS Detection Substrate

To prepare silver nitrate solution, measure 0.0017 grams of AR grade silver nitrate on a weighing balance. Add the weighed powder to 10 milliliters of deionized water and stir the mixture. Draw one milliliter of AR grade ammonia water using a syringe and add it to the silver nitrate solution while stirring, until the solution becomes clear.To prepare 0.2 molar glucose solution, weigh 0.36 grams of glucose powder and add it to 10 milliliters of deionized water. Stir the mixture thoroughly. Next, using a pipette gun, add 30 microliters of the silver ammonia complex into the glucose solution at 30 minute intervals.To synthesize yellow colored silver nanoparticles. To synthesize the PDMS substrate, take five grams of PDMS A solution and add B solution into it, at a ratio of one to 10. Stir the mixture thoroughly.Transfer the mixed PDMS into a square Petri dish and bake it in an 80 degree Celsius oven for two hours. Once cured, use a scalpel to cut the PDMS along the dark grid of the dish, creating small cubes. Next, move the handheld plasma processor back and forth over the PDMS piece for surface plasma treatment.For APTES modification, immerse the surface modified PDMS pieces into 10%APTES solution for 10 hours. Finally, immerse the PDMS substrate into the silver nanoparticle solution for 10 hours. ESEM images showed uniformity in synthesized nanoparticles with diameters between 20 and 50 nanometers.The Surface-Enhanced Raman Scattering signals for fabricated PDMS substrates displayed excellent detection capability, reaching a limit of 10 to the negative 10th molar for R6G with notable enhancement effect. The substrate also showed Thiram detection with clear characteristic peaks, up to 10 to the minus eighth molar. The paste and peel method on the apple surface show the detection of Thiram up to 10 to the minus seventh molar, indicating the effectiveness of the substrate for identifying pesticide residues on fruit surfaces.