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NIR-Active Plasmonic Gold Nanocapsules Synthesized Using Thermally Induced Seed Twinning for Surface-Enhanced Raman Scattering Applications
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2018-10-22 00:00:00 , DOI: 10.1021/acsami.8b14445 Prem Singh 1 , Tobias A. F. König 2, 3 , Amit Jaiswal 1
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2018-10-22 00:00:00 , DOI: 10.1021/acsami.8b14445 Prem Singh 1 , Tobias A. F. König 2, 3 , Amit Jaiswal 1
Affiliation
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Hollow and porous core–shell nanostructures with defined interior nanogaps are of great significance in the field of surface-enhanced Raman scattering (SERS) applications because of the presence of intrinsic electromagnetic (EM) hot spots, multipolar resonances, and multiple facets. Further, nanomaterials having extinction in the near-infrared (NIR) region are particularly important for SERS and biomedical applications, and thus it is highly desirable to synthesize NIR-active plasmonic nanostructures. Herein, we report the synthesis of gold nanocapsules having a solid Au bead as core and a thin-porous rod-shaped shell with extinction in both NIR I and NIR II regions. Thermally induced twinned seeds were used for the silver-free synthesis of pentatwinned Au bead, which served as the foundation for the directed growth of Ag nanorods, which was finally converted to Au nanocapsules following galvanic replacement reaction (GRR). Detailed investigation was carried out to understand the effect of thermal treatment duration in the seed morphology and its subsequent growth to anisotropic Au beads. Ag overgrowth on Au beads yielded uniform [email protected] nanorods whose size can be tuned by varying the Ag precursor. Five different sized [email protected] nanorods were studied, and they were converted to Au nanocapsules following GRR. We explored the size-dependent SERS activity of the prepared Au nanocapsules along with their comparison with solid pentatwinned Au beads and found that the smallest sized Au nanocapsules were the best SERS performers. Finite-difference time-domain simulation revealed the presence of intense EM hot spots in the smallest sized Au nanocapsule and corroborated the experimental SERS data. Finally, we fabricated a simple flexible cellulose-based SERS substrate by using the smallest sized Au nanocapsules and investigated its SERS sensing ability for the detection of 2-napthalenethiol (2-NT), as a model analyte, and were able to achieve its detection down to 1 fM concentration.
中文翻译：
热诱导种子孪晶合成的近红外活性等离子金纳米胶囊，用于表面增强拉曼散射应用
由于存在固有的电磁（EM）热点，多极共振和多个面，具有定义的内部纳米间隙的空心和多孔核-壳纳米结构在表面增强拉曼散射（SERS）应用领域中具有重要意义。此外，在近红外（NIR）区域具有消光作用的纳米材料对于SERS和生物医学应用特别重要，因此，非常需要合成NIR活性等离子体纳米结构。在本文中，我们报道了金纳米胶囊的合成，该纳米胶囊具有固态金珠为核心，并且在NIR I和NIR II区域均具有消光作用的细孔棒状壳。热诱导孪晶种子用于无银合成五键合金珠，这是Ag纳米棒定向生长的基础，经电流置换反应（GRR）最终将其转化为金纳米胶囊。进行了详细的研究，以了解热处理时间对种子形态及其随后生长成各向异性金珠的影响。Ag在Au珠上的过度生长产生了均匀的[受电子邮件保护的]纳米棒，可以通过改变Ag前驱体来调节其大小。研究了五种不同尺寸的[受电子邮件保护的]纳米棒，并在GRR之后将其转化为Au纳米胶囊。我们探索了所制备的金纳米胶囊的大小依赖性SERS活性，并将其与经五氧化碳的固态Au珠进行比较，发现最小尺寸的金纳米胶囊是最佳的SERS表现者。时域有限差分模拟显示最小尺寸的Au纳米胶囊中存在强烈的EM热点，并证实了实验性SERS数据。最后，我们使用最小尺寸的Au纳米胶囊制备了一种简单的基于柔性纤维素的SERS基质，并研究了其对2萘硫酚（2-NT）作为模型分析物的SERS传感能力，并能够实现其检测浓度低至1 fM。
更新日期：2018-10-22
中文翻译：
热诱导种子孪晶合成的近红外活性等离子金纳米胶囊，用于表面增强拉曼散射应用
由于存在固有的电磁（EM）热点，多极共振和多个面，具有定义的内部纳米间隙的空心和多孔核-壳纳米结构在表面增强拉曼散射（SERS）应用领域中具有重要意义。此外，在近红外（NIR）区域具有消光作用的纳米材料对于SERS和生物医学应用特别重要，因此，非常需要合成NIR活性等离子体纳米结构。在本文中，我们报道了金纳米胶囊的合成，该纳米胶囊具有固态金珠为核心，并且在NIR I和NIR II区域均具有消光作用的细孔棒状壳。热诱导孪晶种子用于无银合成五键合金珠，这是Ag纳米棒定向生长的基础，经电流置换反应（GRR）最终将其转化为金纳米胶囊。进行了详细的研究，以了解热处理时间对种子形态及其随后生长成各向异性金珠的影响。Ag在Au珠上的过度生长产生了均匀的[受电子邮件保护的]纳米棒，可以通过改变Ag前驱体来调节其大小。研究了五种不同尺寸的[受电子邮件保护的]纳米棒，并在GRR之后将其转化为Au纳米胶囊。我们探索了所制备的金纳米胶囊的大小依赖性SERS活性，并将其与经五氧化碳的固态Au珠进行比较，发现最小尺寸的金纳米胶囊是最佳的SERS表现者。时域有限差分模拟显示最小尺寸的Au纳米胶囊中存在强烈的EM热点，并证实了实验性SERS数据。最后，我们使用最小尺寸的Au纳米胶囊制备了一种简单的基于柔性纤维素的SERS基质，并研究了其对2萘硫酚（2-NT）作为模型分析物的SERS传感能力，并能够实现其检测浓度低至1 fM。
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