基于Si基沉积拉曼增强活性Au膜的制备与表征

研究了一种新的表面增强拉曼活性Au基底的制备方法,采用无电镀沉积方法,通过HF和HAuCl4的混合溶液对Si片进行处理获得具有不同形貌的Si基Au膜,利用扫描电子显微镜(SEM)分析了基底的表面形态和结构,测定结晶紫分子在基底表面的拉曼光谱。结果表明,Si基Au膜表面的表面增强拉曼散射(SERS)增强随制备时间的增加呈现先增强后减弱的趋势,增强效果优于常用的Au胶体系,是一种非常高效的拉曼活性增强基底。     

C层包覆Ag纳米颗粒基底的表面增强拉曼散射研究

Ag纳米结构是最常用的表面增强拉曼散射(SERS) 活性基底,缺点是Ag的化学稳定性和 生物相容性比较差。为此,利用化学方法合成了一种新型的SERS活性基底—纳米碳层包覆的 Ag(Ag@C)纳米颗粒。利用透射电子显微镜(TEM)和紫外- 可见吸收光谱对制备的核壳结构纳米颗粒进行了表征,并研究了颗粒的SERS活性。结果表明 ,罗丹明6G(R6G)、结晶紫(CV)和孔雀石绿(MG)分子在Ag@C悬浮液中的SERS光谱强度 与在Ag胶中的SERS光谱强度相比显著增强。根据光谱 的变化规律推断,额外的增强来自于化学增强。由于C层的存在,相比于Ag纳米颗粒, Ag@C颗粒的化学稳定性和生物相容性都有所改进。     

应用置换反应制备高效SERS活性基底研究

利用预处理的铝片和铜片还原硝酸银溶液的方法获得了具有不同表面形貌的银纳米结构.扫描电子显微镜(SEM)图表明反应产物分别为花样和树枝状的银纳米结构.以对羟基苯甲酸(PHBA)作为探针分子,对这种新体系的表面增强拉曼散射(SERS)活性进行了研究,发现该体系是一种非常高效的SERS活性增强基底,并且其SERS活性优于用化学方法制备的银胶.本文对这种新型SERS活性基底的增强机制进行了讨论.     

激光烧蚀Ag表面的结构表征及纳米产物的光谱应用

用Nd：YAG激光器对Ag片在二次去离子水中进行烧蚀,用原子力显微镜(AFM)和扫描电子显微镜(SEM)对Ag表面形态进行测量,发现其表面呈现具有nm量级的粗糙度。同时,在Ag片所处的液体中制备出了具有nm尺度“化学纯净”的Ag胶体系。此体系中,Ag纳米颗粒尺度分布均匀,并且具有很好的稳定性。通过用对羟基苯甲酸(PHBA)作为探针分子,对这种纯净Ag胶体系中的表面增强拉曼散射(SERS)进行研究测试发现,这种Ag胶体系是一种非常高效的SERS活性增强基底,对其原因进行了分析。     

蒸发过程对碳纳米管复合结构拉曼增强特性的影响

为了分析探针分子水溶液蒸发过程对三维基底的表面增强拉曼散射(SERS)特性的影响,利用磁控溅射和高温退火的方法制备了银纳米颗粒修饰垂直排列的碳纳米管阵列(Ag/CNTs)三维复合结构样品。采用time-course SERS mapping测试方法,分别以1μmol/L罗丹明6G(R6G)和10-2μmol/L孔雀石绿(MG)作为探针分子,进行了相应的实验。研究表明:随着蒸发时间逐渐增加,探针分子的拉曼信号先增强后减弱。分析其主要原因:探针分子溶液在蒸发过程中,由于毛细力的作用,引起探针分子与三维结构之间"热点"的变化,从而带来电磁场增强特性的变化;此外,聚焦深度和浓度的变化也影响拉曼信号。     

修饰银纳米粒子的石墨烯泡沫镍衬底制备及其SERS活性研究

为了解决表面增强拉曼散射(SERS)衬底的吸附性差、稳定性低以及灵敏度不高的问题,设计了一种沉积银纳米粒子的石墨烯泡沫镍SERS衬底,并进行了实验研究.利用化学气相沉积法在泡沫镍衬底上生长石墨烯,并通过溶液沉积的方法将合成的银纳米粒子沉积在石墨烯泡沫镍衬底表面,烘干后制备成石墨烯泡沫镍修饰银纳米粒子的新型SERS衬底.采用罗丹明6G(R6G)对SERS衬底进行拉曼实验研究,结果表明石墨烯能够较好地淬灭SERS衬底的背景荧光;泡沫镍的独特三维结构能够增大衬底对检测分子的吸附;同时,银纳米粒子也可大幅增强衬底的SERS活性.而修饰了银纳米粒子的石墨烯泡沫镍新型衬底同时具有以上优异特性,是一种具有很大应用潜力的新型SERS衬底.     

自组装法制备团簇Ag纳米结构衬底及其SERS

采用自组装方法,在3-Aminopropyltrimethoxysilane(APS)分子修饰后的玻璃衬底表面,获得了二维Ag纳米结构衬底。在波长为532nm激光激发下,研究了沉积在衬底表面的Rhodamine 6G(Rh6G)分子的拉曼光谱特性。结果表明,制备的二维Ag纳米结构衬底具有强的拉曼增强特性,增强因子可以达到107倍。这说明,在外光场作用下,制备的Ag纳米结构衬底表面能够形成的强局部电磁场分布,可以有效提升探针分子的光谱辐射效率,从而获得高增强拉曼散射。     

Ag纳米粒子修饰多模光纤的拉曼增强特性实验

为了分析研究光纤表面增强拉曼散射(SERS)探针 的拉曼增强特性,采用简单廉价的化学方法制备Ag纳米颗粒修饰 光纤SERS探针,采用罗丹明6G(R6G,Rhodamine 6G)作为探针分子进行了不同浓度R6G溶 液(10－7~10－9M)的拉曼测试实 验和浓度为10－6M的R6G溶液的Time-course SERS Mapping实验,研究了该光纤 SER S探针的拉曼增强特性,制备的光纤SERS 探针样品检测R6G的极限浓度低至10－9M;在Time-course SE RS Mapping实验中,分 析验证了探针分子溶液蒸发过程对光纤 SERS探针的拉曼增强特性的影响。研究表明,由于制备的光纤SERS探针对荧光噪声没有抑 制作用,导致所测得探针分子 的拉曼光谱受探针分子溶液状态、测试方式的极大影响。当溶液充足时(浸泡状态),所测 光谱信号荧光噪声与有效拉曼光 谱信号都比较大;在溶液干燥过程中,所测光谱信号荧光噪声与有效拉曼光谱信号都减少, 但荧光噪声减小幅度远大于拉曼光谱信号。     

基于表面增强拉曼光谱的甲萘威水溶液检测分析

以表面增强试剂OTR202和OTR103作为表面增强拉曼光谱(SERS)的活性基底,探索建立甲萘威水溶液的SERS检测方法。首先对比分析了甲萘威水溶液的普通拉曼光谱与SERS。然后分析了表面增强试剂与待测样本的加入量对甲萘威水溶液的SERS的影响。最后分析了质量浓度在0.1~15.0 mg/L范围内的甲萘威水溶液的SERS,并以1374 cm-1处的特征峰强度与甲萘威水溶液浓度进行线性回归,得到线性方程为y=414.5x+481.59,决定系数R2=0.9864。试验结果表明该研究方法对甲萘威水溶液的检测限可达到0.1 mg/L,说明以表面增强试剂OTR202和OTR103为SERS活性基底的SERS检测方法可用于水中甲萘威残留检测。     

自组装法制备团簇Ag纳米结构衬底及其SERS

采用自组装方法,在3-Aminopropyltrimethoxy silane(APS)分子修饰后的玻璃衬底表面,获得了二维Ag纳 米结构衬底。在波长为532nm激光激发下,研究了沉积在衬底表面的 Rhodamine 6G(Rh6G)分子的拉曼光谱特性。结 果表明,制备的二维Ag纳米结构衬底具有强的拉曼增强特性,增强因子可以达到 10⁷ 倍。这说明,在外光场作用下,制备的Ag纳米结构衬底表面能够形成的强局部电磁场分布, 可以有效提升探针分子的光谱辐射效率,从而获得高增强拉曼散射。     

多种形貌纳米银的电化学制备及其表面增强拉曼光谱研究

采用电化学沉积的方法制备出球状、棒状、树枝状、立方体状、带孔洞的多面体状的纳米银.扫描电镜的显微观察结果显示,沉积电压不仅影响纳米银的尺寸大小而且对形貌也有重要影响.通过对球状和树枝状纳米银进行的表面增强拉曼光谱(surface-enhanced raman scattering,SERS)的应用研究表明,用电化学沉积...     

柔性表面增强拉曼光谱芯片制备

柔性表面增强拉曼光谱(SERS)基底具有灵活形变的特点,适合不规则曲面的原位检测,甚至可以直接进行擦拭取样的检测。对不同反射率的衬底进行仿真分析和实验测试,可以看到衬底的反射率对拉曼信号的收集有极大的影响。在波长为532 nm的光激发铝箔具有高反射率,因此选择铝箔作为衬底,采用银溶胶滴铸法制备柔性SERS芯片。实验通过控制溶剂成分,利用表面张力梯度引起向内马兰哥尼(Marangoni)流动以抑制咖啡环的产生,可以改善纳米粒子的分布均匀性。拉曼测试结果表明,SERS芯片的增强因子高达1.32×10⁸,对R6G溶液的检测限低至1×10^-11mol,同时芯片表现出良好的信号均匀性。     

Fabrication of a network structure SERS substrate and the application in ultra-sensitive crystal violet detection

A network structure surface-enhanced Raman scattering(SERS)-active substrate is fabricated by adding Ag sol dropwise on adhesive tape.Scanning electron microscope(SEM) is employed to characterize the structure of the as-prepared substrate.The substrate shows great SERS enhancement ability and good uniformity by using p-aminothiophenol(PATP) as probe molecules.The detection of crystal violet(CV) in aqueous solution is demonstrated,and the detection limit is as low as 10-12M with the aid of the substrate.The results indicate that the proposed method is a potential approach for the fabrication of SERS substrates.     

癸烷硫醇修饰的金/银SERS衬底用于PCB-77检测的研究

通过模板法制备了强SERS活性的“球加片”Au/Ag纳米结构阵列,并利用这种纳米衬底对PCB-77分子的SERS光谱进行了研究。结果表明,尽管该纳米结构能够检测到PCB-77分子的SERS特征峰,但信噪比低。利用癸烷硫醇中的巯基与贵金属之间相互作用,实现了癸烷硫醇分子对纳米结构表面的功能化修饰,研究发现此时PCB-77分子的SERS光谱质量得到了明显改善。并且,这种“球加片”衬底的癸烷硫醇分子最优修饰时间为36小时,利用经36小时修饰后的纳米衬底,极大地提高了PCB-77的SERS光谱特征峰的强度。     

Near-Infrared II Plasmonic Au@Au–Ag Dot-in-Cubic Nanoframes for In Vivo Surface-Enhanced Raman Spectroscopic Detection and Photoacoustic Imaging

Near-infrared II (NIR-II) plasmonic noble-metallic nanostructures are highly desirable for in vivo photodiagnostics because of their multiple functionalities and deep-tissue optical imaging capability. Herein, a novel class of Au@Au–Ag dot-in-cubic nanoframes (DCFs) comprising a solid Au core and a Au–Ag alloy shell with a wall hole on each side face is reported, which exhibit remarkable plasmonic properties spectrally tunable beyond 1400 nm while maintaining a small size. The synthesis of Au@Au–Ag DCFs is principally based on the facet-selective etching of Ag atoms and co-deposition of Au and Ag atoms on the edges and corners of Au@Ag dot-in-cubes. The geometry (e.g., edge length and wall hole size) can be controllably tailored by simply varying the silver nitrate and chloroauric acid concentrations. Superior in vitro and in vivo NIR-II photoacoustic imaging performances of Au@Au–Ag DCFs are demonstrated. Additionally, remarkable NIR-II surface-enhanced Raman spectroscopy (SERS) activity of Au@Au–Ag DCFs is evidenced with the maximum NIR-II SERS enhancement occurring at a plasmon resonance wavelength blue-shifting from the incident laser wavelength and an excellent effective detection depth. Finally, the potential of the developed Au@Au–Ag DCFs is highlighted for in vivo NIR-II SERS detection of microtumors in animals.     

Silver-Polymer Composite Stars: Synthesis and Applications

Colloidal "silver stars" were synthesized upon poly(lactic-co-glycolic) acid nanosphere templates via a facile two-step silver reduction method. Myriad dendrimer-like Ag star morphologies were synthesized by varying the amount of poly(vinyl alcohol) and trisodium citrate used during silver reduction. Scanning electron microscopy studies revealed that star-shaped silver-polymer composites possessing nanoscopic, fractal morphologies with diameters ranging from 500 nm to 7 μm were produced. These composites have broad applications from antibacterial agents to catalysis; two such applications were tested here. Surface-enhanced Raman spectroscopy (SERS) studies showed multiple hot spots of SERS activity within a single star. Electrochemical catalysis experiments demonstrated the feasibility of using the silver stars instead of platinum for the oxygen reduction reaction in alkaline fuel cells.     

Arrays of Cone‐Shaped ZnO Nanorods Decorated with Ag Nanoparticles as 3D Surface‐Enhanced Raman Scattering Substrates for Rapid Detection of Trace Polychlorinated Biphenyls

A new, highly sensitive and uniform three‐dimensional (3D) hybrid surface‐enhanced Raman scattering (SERS) substrate has been achieved via simultaneously assembling small Ag nanoparticles (Ag‐NPs) and large Ag spheres onto the side surface and the top ends of large‐scale vertically aligned cone‐shaped ZnO nanorods (ZnO‐NRs), respectively. This 3D hybrid substrate manifests high SERS sensitivity to rhodamine and a detection limit as low as 10^?11 M to polychlorinated biphenyl (PCB) 77—a kind of persistent organic pollutants as global environmental hazard. Three kinds of inter‐Ag‐NP gaps in 3D geometry create a huge number of SERS “hot spots” that mainly contribute to the high SERS sensitivity. Moreover, the supporting chemical enhancement effect of ZnO‐NRs and the better enrichment effect ascribed to the large surface area of the substrate also help to achieve a lower detection limit. The arrays of cone‐shaped ZnO‐NRs decorated with Ag‐NPs on their side surface and large Ag spheres on the top ends have potentials in SERS‐based rapid detection of trace PCBs.     

Silver Stars: Silver–Polymer Composite Stars: Synthesis and Applications (Adv. Funct. Mater. 9/2011)

Colloidal “silver stars” were synthesized upon poly(lactic‐co‐glycolic) acid nanosphere templates via a facile two‐step silver reduction method. Myriad dendrimer‐like Ag star morphologies were synthesized by varying the amount of poly(vinyl alcohol) and trisodium citrate used during silver reduction. Scanning electron microscopy studies revealed that star‐shaped silver–polymer composites possessing nanoscopic, fractal morphologies with diameters ranging from 500 nm to 7 μm were produced. These composites have broad applications from antibacterial agents to catalysis; two such applications were tested here. Surface‐enhanced Raman spectroscopy (SERS) studies showed multiple hot spots of SERS activity within a single star. Electrochemical catalysis experiments demonstrated the feasibility of using the silver stars instead of platinum for the oxygen reduction reaction in alkaline fuel cells.     

Near‐Field Enhanced Plasmonic‐Magnetic Bifunctional Nanotubes for Single Cell Bioanalysis

Near‐field enhanced bifunctional plasmonic‐magnetic (PM) nanostructures consisting of silica nanotubes with embedded solid nanomagnets and uniformly dual‐surface‐coated plasmonic Ag nanoparticles (NPs) are rationally synthesized. The solid embedded sections of nanotubes provide single‐molecule sensitivity with an enhancement factor up to 7.2 × 10⁹ for surface‐enhanced Raman scattering (SERS). More than 2× SERS enhancement is observed from the hollow section compared to the solid section of the same nanotube. The substantial SERS enhancement on the hollow section is attributed to the dual‐sided coating of Ag NPs as well as the near‐field optical coupling of Ag NPs across the nanotube walls. Experimentation and modeling are carried out to understand the dependence of SERS enhancement on the NP sizes, junctions, and the near field effects. By tuning the aspect ratio of the embedded nanomagnets, the magnetic anisotropy of nanotubes can be readily controlled to be parallel or vertical to the long directions for nano‐manipulation. Leveraging the bifunctionality, a nanotube is magnetically maneuvered to a single living mammalian cell amidst many and its membrane composition is analyzed via SERS spectroscopy.     

Near‐Infrared SERS Nanoprobes with Plasmonic Au/Ag Hollow‐Shell Assemblies for In Vivo Multiplex Detection

For the effective application of surface‐enhanced Raman scattering (SERS) nanoprobes for in vivo targeting, the tissue transparency of the probe signals should be as high as it can be in order to increase detection sensitivity and signal reproducibility. Here, near‐infrared (NIR)‐sensitive SERS nanoprobes (NIR SERS dots) are demonstrated for in vivo multiplex detection. The NIR SERS dots consist of plasmonic Au/Ag hollow‐shell (HS) assemblies on the surface of silica nanospheres and simple aromatic Raman labels. The diameter of the HS interior is adjusted from 3 to 11 nm by varying the amount of Au³⁺ added, which results in a red‐shift of the plasmonic extinction of the Au/Ag nanoparticles toward the NIR (700–900 nm). The red‐shifted plasmonic extinction of NIR SERS dots causes enhanced SERS signals in the NIR optical window where endogenous tissue absorption coefficients are more than two orders of magnitude lower than those for ultraviolet and visible light. The signals from NIR SERS dots are detectable from 8‐mm deep in animal tissues. Three kinds of NIR SERS dots, which are injected into live animal tissues, produce strong SERS signals from deep tissues without spectral overlap, demonstrating their potential for in vivo multiplex detection of specific target molecules.