基于三维纳米阵列结构的表面增强拉曼技术研究及其在痕量铀酰离子探测中的应用

表面增强拉曼散射(SERS)是一种新型痕量表征技术，其灵敏度高、样品用量少、特征谱易辨识，尤其适用于铀酰离子等危化品的探测。在过去十几年里, 纳米材料和纳米技术在新兴技术和SERS的应用方面获得了长足发展，将先进的纳米制造技术引入了SERS领域。本文总结了利用光刻、原子层沉积等技术，开发了一系列高质量的三维阵列纳米材料作为SERS基底，并应用于痕量铀酰离子的检测。其中，以Al₂O₃、HfO₂等惰性氧化物包裹修饰的银纳米棒三维阵列作为基底，灵敏度高，稳定性好，根据不同特征的拉曼振动频谱，可识别多个不同种态的铀酰离子，检出限低至nmol/L，具有潜在的实际应用价值。     

Diverse bio-sensing and therapeutic applications of plasmon enhanced nanostructures

Substantial advancements have been observed over the years in the research and development of Localized Surface Plasmon Resonance (LSPR). A variety of current and future applications involving anisotropic plasmonic nanoparticles include biosensors, photothermal therapies, photocatalysis, and various other fields. Amongst various other applications, plasmonic enhancements are deployed in Surface Enhanced Raman Spectroscopy (SERS) mediated bio-sensing, absorption spectroscopy based analyte quantification, and fluorescence spectroscopy-based biomolecular detection up to femtomolar level and even on the level of single molecules. LSPR based healthcare diagnostics and therapeutics have grown much faster than expected, with an increased number of published original research articles and reviews. Despite the extensive literature available, a comprehensive review with a focused emphasis on recent advances in the field of plasmonic particle anisotropy, plasmonic nanostructure, plasmonic coupling mediated enhanced LSPR intensity and their diverse applications in biosensing is needed. This article focuses on LSPR properties of anisotropic nanostructures like spherical gold nanoparticles (AuNP), gold nanorod (AuNR), gold nanostar (AuNs), gold nanorattles (AuNRT), gold nanoholes (AuNH), dimeric nanostructures and their role in plasmonic enhancements for targeted biosensing and therapeutic research. The contemporary state of the art biosensing development around SERS has also been discussed. A detailed literature analysis of recent development in micro-surgery, photothermal tumor killing, biosensor development for detection up to single molecule level, high-efficiency drug delivery are covered in this article. Furthermore, recent and advanced technologies including Spatially Offset Raman Spectroscopy (SORS), Surface Enhanced Resonance Raman Spectroscopy (SERRS), and Surface Enhanced Spatially Offset Raman Spectroscopy (SESORS) are presented citing their importance in biosensing. We complement this review article with relevant theoretical frameworks to understand finer nuances within the literature that is discussed.     

Microwave-assisted green synthesis of Ag/reduced graphene oxide nanocomposite as a surface-enhanced Raman scattering substrate with high uniformity

A nanocomposite of silver nanoparticles/reduced graphene oxide (Ag/rGO) has been fabricated as a surface-enhanced Raman scattering (SERS) substrate owing to the large surface area and two-dimensional nanosheet structure of rGO. A facile and rapid microwave-assisted green route has been used for the formation of Ag nanoparticles and the reduction of graphene oxide simultaneously with L-arginine as the reducing agent. By increasing the cycle number of microwave irradiation from 1 and 4 to 8, the mean diameters of Ag nanoparticles deposited on the surface of rGO increased from 10.3 ± 4.6 and 21.4 ± 10.5 to 41.1 ± 12.6 nm. The SERS performance of Ag/rGO nanocomposite was examined using the common Raman reporter molecule 4-aminothiophenol (4-ATP). It was found that the Raman intensity of 4-ATP could be significantly enhanced by increasing the size and content of silver nanoparticles deposited on rGO. Although the Raman intensities of D-band and G-band of rGO were also enhanced simultaneously by the deposited Ag nanoparticles which limited the further improvement of SERS detection sensitivity, the detectable concentration of 4-ATP with Ag/rGO nanocomposite as the SERS substrate still could be lowered to be 10⁻¹⁰ M and the enhancement factor could be increased to 1.27 × 10¹⁰. Furthermore, it was also achievable to lower the relative standard deviation (RSD) values of the Raman intensities to below 5%. This revealed that the Ag/rGO nanocomposite obtained in this work could be used as a SERS substrate with high sensitivity and homogeneity.     

高温高压水中镍基合金表面氧化膜的原位表面增强型拉曼光谱

采用表面增强型拉曼光谱方法原位研究了镍基合金在高温高压水环境中的腐蚀行为及其表面生成氧化膜.Ni-5Cr-8Fe表面氧化膜的拉曼光谱存在三个拉曼峰,位于540 cm-1,610 cm-1和670 cm-1.610 cm-1峰的出现表明了氧化膜中存在Cr2 O3.540 cm-1峰则说明氧化膜中含有Cr2 O3或NiO或两者的混合物.670 cm-1峰对应于FeCr2O4尖晶石的生成.Ni-10Cr-8Fe的表面氧化膜由Cr2 O3、FeCr2O4构成,可能含有一定的NiO.Ni-10Cr和Ni-20Cr的表面氧化膜主要为Cr2 O3,没有发现尖晶石相的存在.随着合金中铬含量的增加,表面氧化膜中Cr2O3的含量增加,NiO成分减少.     

基于银纳米颗粒的HCPCFSERS传感系统优化设计

银纳米颗粒与光子晶体光纤、表面增强拉曼散射效应结合而成的PCF SERS传感器得到了科研界的广泛关注.而PCF结构、SERS基底的性能是传感器的重要影响因素.为了进一步提高SERS PCF传感器的性能,通过研究对比PCF和SERS基底结构参数对传感性能的影响,设计出适用于PCF SERS传感的空芯PCF以及SERS基底的结构参数.通过数值计算,设计的空芯PCF空气填充率为56.30%,当激发光波长785 nm时存在光子带隙,并能够实现单模传输.而半径为38 nm的银纳米球在间距为0.7 nm时能够产生最大的SERS增强因子.研究证明,设计的空芯PCF在785 nm输入波长下既能够基模传输激发光,又能够为SERS提供理想的活性面积,而且银纳米颗粒的形状、尺寸、间距对SERS性能影响严重,而且与入射波长有很强的依赖关系.     

Double‐Walled Au Nanocage/SiO2 Nanorattles: Integrating SERS Imaging,Drug Delivery and Photothermal Therapy

In this work, a novel type of nanomedical platform, the double‐walled Au nanocage/SiO₂ nanorattle, is successfully fabricated by combining two “hollow‐excavated strategies”—galvanic replacement and “surface‐protected etching”. The rational design of double‐walled nanostructure based on gold nanocages (AuNCs) and hollow SiO₂ shells functionalized respectively with p‐aminothiophenol (pATP) and Tat peptide simultaneously renders the nanoplatforms three functionalities: 1) the whole nanorattle serves as a high efficient drug carrier thanks to the structural characteristics of AuNC and SiO₂ shell with hollow interiors and porous walls; 2) the AuNC with large electromagnetic enhancement acts as a sensitive surface‐enhanced Raman scattering (SERS) substrate to track the internalization process of the nanorattles by human MCF‐7 breast cancer cells, as well as an efficient photothermal transducer for localized hyperthermia cancer therapy due to the strong near‐infrared absorption; 3) Tat‐functionalized SiO₂ shell not only improves biocompatibility and cell uptake efficiency resulting in enhanced anticancer efficacy but also prevents the AuNCs from aggregation and provides the stability of AuNCs so that the SERS signals can be used for cell tracking in high fidelity. The reported chemistry and the designed nanostructures should inspire more interesting nanostructures and applications.     

Selective Capture and Quick Detection of Targeting Cells with SERS‐Coding Microsphere Suspension Chip

Circulating tumor cells (CTCs) captured from blood fluid represent recurrent cancers and metastatic lesions to monitor the situation of cancers. We develop surface‐enhanced Raman scattering (SERS)‐coding microsphere suspension chip as a new strategy for fast and efficient capture, recovery, and detection of targeting cancer cells. Using HeLa cells as model CTCs, we first utilize folate as a recognition molecule to be immobilized in magnetic composite microspheres for capturing HeLa cells and attaining high capturing efficacy (up to 95%). After capturing cells, the composite microsphere, which utilizes a disulfide bond as crosslinker in the polymer shell and as a spacer for linking folate, can recycle 90% cells within 20 min eluted by glutathion solution. Taking advantage of the SERS with fingerprint features, we characterize captured/recovered cells with the unique signal of report‐molecule 4‐aminothiophenol through introducing the SERS‐coding microsphere suspension chip to CTCs. Finally, the exploratory experiment of sieving cells shows that the magnetic composite microspheres can selectively capture the HeLa cells from samples of mixed cells, indicating that these magnetic composite microspheres have potential in real blood samples for capturing CTCs.     

一种中空金/银双金属纳米颗粒的制备及其SERS性能

以银纳米颗粒为牺牲模板,利用Ag和HAu Cl4之间的置换反应,结合柠檬酸钠同步还原的方法制备了一种中空金/银双金属纳米颗粒。通过对颗粒形貌及局域表面等离子体共振(LSPR)的分析,初步研究了此类金/银纳米颗粒的生长机理,并对影响反应的因素进行了探讨。结果表明,通过控制反应条件可以实现对LSPR的精密调控。该类金/银双金属纳米颗粒可用作为SERS基底,苯硫酚在其表面增强因子可达107,并具有良好的信号重现性。该基底用于atto610标记的生物素与亲和素的SERS检测,检测限可达80 pg/m L。