Zhao Xingjuan, Luo Xiaojun, Bazuin C Geraldine, Masson Jean-Francois
Département de chimie, Centre québécois des matériaux fonctionnels (CQMF) and Regroupement québécois des matériaux de pointe (RQMP), Université de Montréal, C.P. 6128 Succ. Centre-Ville, Montréal, Quebec H3C 3J7, Canada.
Jiangsu Key Laboratory of New Power Batteries, Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, College of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210097, P.R. China.
ACS Appl Mater Interfaces. 2020 Dec 9;12(49):55349-55361. doi: 10.1021/acsami.0c15311. Epub 2020 Nov 25.
It is challenging to fabricate plasmonic nanosensors on high-curvature surfaces with high sensitivity and reproducibility at low cost. Here, we report a facile and straightforward strategy, based on an growth technique, for fabricating glass nanofibers covered by asymmetric gold nanoparticles (AuNPs) with tunable morphologies and adjustable spacings, leading to much improved surface-enhanced Raman scattering (SERS) sensitivity because of hotspots generated by the AuNP surface irregularities and adjacent AuNP coupling. First, nanosensors covered with uniform and well-dispersed citrate-capped spherical AuNPs were constructed using a polystyrene--poly(4-vinylpyridine) (PS-P4VP, with 33 mol % P4VP content and 61 kg/mol total molecular weight) block copolymer brush-layer templating method, and then, the deposited AuNPs were grown to asymmetric AuNPs. AuNP morphologies and hence the optical characteristics of AuNP-covered glass nanofibers were easily controlled by the choice of experimental parameters, such as the growth time and growth solution composition. In particular, tunable AuNP average diameters between about 40 and 80 nm with AuNP spacings between about 50 and 1 nm were achieved within 15 min of growth. The SERS sensitivity of branched AuNP-covered nanofibers (3 min growth time) was demonstrated to be more than threefold more intense than that of the original spherical AuNP-covered nanofibers using a 633 nm laser. Finite-difference time-domain simulations were performed, showing that the electric field enhancement is highest for intermediate AuNP diameters. Furthermore, SERS applications of these nanosensors for HO detection and pH sensing were demonstrated, offering appealing and promising candidates for real-time monitoring of extra/intracellular species and .
在高曲率表面上以低成本制造具有高灵敏度和可重复性的等离子体纳米传感器具有挑战性。在此,我们报告了一种基于生长技术的简便直接策略,用于制造由形态可调且间距可调节的不对称金纳米颗粒(AuNP)覆盖的玻璃纳米纤维,由于AuNP表面不规则性和相邻AuNP耦合产生的热点,导致表面增强拉曼散射(SERS)灵敏度大大提高。首先,使用聚苯乙烯 - 聚(4 - 乙烯基吡啶)(PS - P4VP,P4VP含量为33摩尔%,总分子量为61千克/摩尔)嵌段共聚物刷层模板法构建覆盖有均匀且分散良好的柠檬酸盐包覆球形AuNP的纳米传感器,然后,将沉积的AuNP生长为不对称AuNP。通过选择实验参数,如生长时间和生长溶液组成,可以轻松控制AuNP的形态以及因此AuNP覆盖的玻璃纳米纤维的光学特性。特别是,在15分钟的生长时间内实现了约40至80nm的可调AuNP平均直径以及约50至1nm的AuNP间距。使用633nm激光,分支AuNP覆盖的纳米纤维(生长3分钟)的SERS灵敏度被证明比原始球形AuNP覆盖的纳米纤维高出三倍以上。进行了时域有限差分模拟,结果表明中间AuNP直径的电场增强最高。此外,还展示了这些纳米传感器在HO检测和pH传感方面的SERS应用,为细胞外/细胞内物质的实时监测提供了有吸引力且有前景的候选方案。