表面等离子体受激辐射放大领结型纳米天线的SERS单分子探测(英文)

基于表面等离激子受激辐射放大原理,提出了一种应用于表面增强拉曼散射(SERS)单分子探测的领结型纳米天线结构。采用有限元方法(FEM)研究其局域表面等离子体共振(LSPR)和SERS特性。结果表明,该领结型纳米天线的局域表面等离子体共振强度和局域电场强度得到明显的增强,其散射截面为非表面等离激子受激辐射放大领结型纳米天线的1.1×104倍,局域电场强度为1×102倍。同时,该领结型纳米天线的表面增强拉曼散射增强因子最大达到1016,足以进行精确的单分子探测;整个纳米天线表面的增强因子也可达到1012,足以应用于单个生物分子的探测。     

等离激元共振增强多晶硅薄膜太阳电池性能研究

采用磁控溅射方法,在多晶硅薄膜太阳电池表面沉积了不同粒径大小的Au纳米粒子,利用粒径大小可调控的Au纳米粒子的局域表面等离激元共振增强效应(LSPR),对入射光中的可见光区域实现“光俘获”;采用UV-vis吸收光谱对LSPR进行了研究,结果表明,LSPR能够有效拓展Au纳米粒子的光谱响应范围(400～800 nm),并且,随着Au纳米粒子粒径的增大,LSPR共振吸收峰呈现出明显“红移”;同时,通过SERS表征,证实LSPR能够有效增强Au纳米粒子周围的局域电磁场强度;最后,多晶硅太阳电池的J-V特性曲线表明,当Au纳米粒子溅射时间为50 s时,多晶硅太阳电池光电转换效率(η)最高为14.8％,比未修饰Au纳米粒子的电池η提高了42.3％.     

多元等离子体共振纳米结构的飞秒激光加工与拉曼检测应用

以多元金属纳米薄膜(金、银)为基底,利用飞秒激光加工技术制备得到多元等离子体纳米结构,并研究了其局域表面等离子体共振效应(Local Surface Plasmon Resonance,LSPR)和表面增强拉曼散射(Surface Enhanced Raman Scattering,SERS)性能。利用时域有限差分(Finite Difference Time Domain,FDTD)软件模拟了不同情况下(单层金膜、金银双层金属薄膜的平面以及阵列结构)的电场分布情况。根据仿真结果,相较于平面金属膜来说,飞秒激光制备的微纳结构阵列附近区域产生电磁场增强,集中在结构边缘处,且其强度变化与预期结果基本保持一致。此外,使用浓度为10-4 M和10-6 M的罗丹明(R6G)溶液进行SERS性能测试。测试的结果表明,单层平面金膜基本没有SERS峰值信号出现,而单层金膜上制备的等离子体纳米结构附近出现峰值信号,双层金属薄膜上制备的等离子体纳米结构展现出更高的SERS峰值信号。多元金属等离子体纳米结构展示出更强的局域表面等离子体共振效应,从而在表面增强拉曼散射、光催化、生物传感等领域具有广泛的应用。     

金属纳米二聚体结构的局域表面等离子体激元共振特性研究

将金属纳米粒子二聚体结构作为光学谐振腔,采用 时域有限差分(FDTD)法仿真模拟了一种新型局域表面等离子体激光器(SPASER)。 使用洛伦兹复介电常数模型研究二聚体的增益介质特性,探讨了二聚体结构中 两个纳米局域表面等离子体激元共振(LSPR)以及相互作用机制,进一步研究了 LSPR相互作用对SPASER的局域场增强的影响。 模拟结果表明,相比较单纳米颗粒SPASER,LSPR的相互作用使得二聚体SPASER的局域电场显著 增强,增强因子最 大可以相差27倍。本文研究为纳米光学器件尤其是激光器件的设计提 供了依据。LSPR效应的 研究可以用于探索一些光与物质相互作用的极限效 应,从而为有源光子线路、生物传感以及量子信息处理等研究开辟道路。     

一种新的具有双面活性的SERS基底

用二次氧化的方法制得了孔径均一、排列规则的阳极氧化铝模板(AAO,anodic aluminumoxide).利用磁控溅射的方法,银纳米颗粒被溅射在模板的表面以及孔洞里面,在模板的一面形成一层粗糙的银表面,当把模板放入一定浓度的NaOH溶液中,反面的Al2O3模板被部分地溶解后露出针尖状的银纳米线阵列.用结晶紫作为探针分子,在粗糙银表面(正面)和针尖状的银纳米线阵列面(反面)得到了不同的表面增强拉曼散射(SERS,surface enhanced Raman scattering)光谱,从而证明了两面具有不同的SERS机制.分析表明:正面粗糙的银表面是吸附增强,而反面在存在吸附增强的同时起主要作用的是针尖状的银纳米线阵列构成的天线模型所产生的非吸附的增强.针尖末端的曲率半径极小,会产生极强的局域电磁场,处于这个场中的分子的信号就被大大增强了.     

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。     

金纳米球壳结构局域表面等离子体共振调谐特性

理论研究了金纳米球壳结构局域表面等离子体共振(LSPR)的调谐特性。结果表明,对于固定内径的球壳结构,利用杂化效应使得球壳结构可通过改变其厚度实现LSPR峰位的调控,并可保持较窄的谱宽;而对于不同内径的球壳,在LSPR调控过程中,随壳层厚度与球壳内半径比值的减小,吸收光谱在消光光谱中所占比例增大。不仅如此,利用杂化效应进行偶极峰位调控时所能获得的峰位调控范围与球壳内径有关,内径越大,所能获得的偶极峰位调控范围越大。     

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.     

Ag掺杂浓度对ZnO纳米花荧光增强的影响

采用水浴与光照相结合的方法制备了Ag/ZnO纳米复 合结构,研究了不同Ag掺杂浓度对 ZnO发光强度的影响。通过X射线衍射(XRD)、扫描电子显微镜(SEM)和光致发光 (PL)光谱对Ag/ZnO纳米复合物的结构、形貌和光学性能进行了研究。SEM表明,由水浴法制 得的ZnO纳米花结构长约1.0μm,直径为200nm左右。XRD结果显示,Ag掺杂后Ag/ZnO 纳米复合结构衍射峰的强度都增强,当掺杂浓度为0.153wt%时,在38.28°出现了Ag₂O的衍射峰。PL表明,Ag浓度极大影响了ZnO紫外发光强度。当Ag的掺杂 浓度为0.051wt% 时,Ag/ZnO纳米复合结构具有最强的紫外发射强度,同未掺杂的ZnO相比,紫外发光强度提 高了11倍。研究结果表明,利用Ag纳米颗粒的局域表面等离子共振(LSPR)特性增强了ZnO纳 米结构的荧光强度,从而提高了荧光检测的灵敏度。     

树枝状Ag基底的制备及其SERS活性研究

研究了一种表面增强拉曼散射(SERS)活性Ag基底的制备新方法。通过电化学方法和液相生长方法相结合在金属Al表面制备SERS活性Ag膜。用扫描电子显微镜(SEM)表征Ag膜的表面形貌,以结晶紫(C25 H30N3Cl·H2O)为拉曼探针分子,研究了基底的SERS增强效果。研究表明:结晶紫分子吸附在Ag膜表面的SERS强度随电沉积时间的增加呈现先增强后减弱的趋势;进一步的Ag增强剂和引发剂的混合溶液对电沉积Ag膜的浸泡处理可以调节基底Ag膜的结构形态,增强电沉积基底Ag膜的SERS活性。     

金纳米颗粒增强富硅氮化硅发光特性的研究

采用时域有限差分(FDTD)方法,对Au纳米颗粒的尺寸和形貌对于其光学特性的影响进行了系统的理论研究。通过采用等离子体增强化学气相沉积(PECVD)、晶化处理、电子束蒸发和高温退火等工艺,制备基于局域表面等离子共振(LSPR)效应的富硅氮化硅发光芯片。利用拉曼光谱仪、扫描电子显微镜(SEM)、奥林巴斯显微镜等对不同结构Au纳米颗粒富硅氮化硅发光器件的特性进行了表征。研究表明,通过对Au纳米颗粒的大小、形状和分布合理优化,富硅氮化硅芯片的发光强度在570nm波长附近提升了7倍,增强峰的位置红移了10nm。     

DNA‐Directed Self‐Assembly of Core‐Satellite Plasmonic Nanostructures: A Highly Sensitive and Reproducible Near‐IR SERS Sensor

The excitation of surface plasmons in metallic nanostructures provides an opportunity to localize light at the nanoscale, well below the scale of the wavelength of the light. The high local electromagnetic field intensities generated in the vicinity of the nanostructures through this nanofocusing effect are exploited in surface enhanced Raman spectroscopy (SERS). At narrow interparticle gaps, so‐called hot‐spots, the nanofocusing effect is particularly pronounced. Hence, the engineering of substrates with a consistently high density of hot‐spots is a major challenge in the field of SERS. Here, a simple bottom‐up approach is described for the fabrication of highly SERS‐active gold core‐satellite nanostructures, using electrostatic and DNA‐directed self‐assembly. It is demonstrated that well‐defined core‐satellite gold nanostructures can be fabricated without the need for expensive direct‐write nanolithography tools such as electron‐beam lithography (EBL). Self‐assembly also provides excellent control over particle distances on the nanoscale. The as‐fabricated core‐satellite nanostructures exhibit SERS activities that are superior to commercial SERS substrates in signal intensity and reproducibility. This also highlights the potential of bottom‐up self‐assembly strategies for the fabrication of complex, well‐defined functional nanostructures with future applications well beyond the field of sensing.     

In situ Characterization of SiO2 Nanoparticle Biointeractions Using BrightSilica

By adding a gold core to silica nanoparticles (BrightSilica), silica‐like nanoparticles are generated that, unlike unmodified silica nanoparticles, provide three types of complementary information to investigate the silica nano‐biointeraction inside eukaryotic cells in situ. Firstly, organic molecules in proximity of and penetrating into the silica shell in live cells are monitored by surface‐enhanced Raman scattering (SERS). The SERS data show interaction of the hybrid silica particles with tyrosine, cysteine and phenylalanine side chains of adsorbed proteins. Composition of the biomolecular corona of BrightSilica nanoparticles differs in fibroblast and macrophage cells. Secondly, quantification of the BrightSilica nanoparticles using laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) micromapping indicates a different interaction of silica nanoparticles compared to gold nanoparticles under the same experimental conditions. Thirdly, the metal cores allow the investigation of particle distribution and interaction in the cellular ultrastructure by cryo nanoscale X‐ray tomography (cryo‐XT). In 3D reconstructions the assumption is confirmed that BrightSilica nanoparticles enter cells by an endocytotic mechanism. The high SERS intensities are explained by the beneficial plasmonic properties due to agglomeration of BrightSilica. The results have implications for the development of multi‐modal qualitative and quantitative characterization in comparative nanotoxicology and bionanotechnology.     

Gold Nanoframeworks with Mesopores for Raman–Photoacoustic Imaging and Photo‐Chemo Tumor Therapy in the Second Near‐Infrared Biowindow

Gold‐based nanostructures with tunable wavelength of localized surface plasmon resonance (LSPR) in the second near‐infrared (NIR‐II) biowindow receive increasing attention in phototheranostics. In view of limited progress on NIR‐II gold nanostructures, a particular liposome template‐guided route is explored to synthesize novel gold nanoframeworks (AuNFs) with large mesopores (≈40 nm) for multimodal imaging along with therapeutic robustness. The synthesized AuNFs exhibit strong absorbance in NIR‐II region, affording their capacity of NIR‐II photothermal therapy (PTT) and photoacoustic (PA) imaging for deep tumors. Functionalization of AuNFs with hyaluronic acid (HA) endows the targeting capacity for CD44‐overexpressed tumor cells while gatekeeping doxorubicin (DOX) loaded into mesopores. Conjugation of Raman reporter 4‐aminothiophenol (4‐ATP) onto AuNFs yields a surface‐enhanced Raman scattering (SERS) fingerprint for Raman spectroscopy/imaging. In vivo evaluation of HA‐4‐ATP‐AuNFs‐DOX on tumor‐bearing xenografts demonstrates its high efficacy in eradication of solid tumors in NIR‐II under PA–Raman dual image‐guided photo‐chemotherapy. Thus, current AuNFs offer versatile capabilities for phototheranostics.     

Spatial Analysis of Metal–PLGA Hybrid Microstructures Using 3D SERS Imaging

The incorporation of gold nanoparticles in biodegradable polymeric nanostructures with controlled shape and size is of interest toward different applications in nanomedicine. Properties of the polymer such as drug loading and antibody functionalization can be combined with the plasmonic properties of gold nanoparticles, to yield advanced hybrid materials. This study presents a new way to synthesize multicompartmental microgels, fibers, or cylinders, with embedded anisotropic gold nanoparticles. Gold nanoparticles dispersed in an organic solvent can be embedded within the poly(lactic‐co‐glycolic acid) (PLGA) matrix of polymeric microstructures, when prepared via electrohydrodynamic co‐jetting. Prior functionalization of the plasmonic nanoparticles with Raman active molecules allows for imaging of the nanocomposites by surface‐enhanced Raman scattering (SERS) microscopy, thereby revealing nanoparticle distribution and photostability. These exceptionally stable hybrid materials, when used in combination with 3D SERS microscopy, offer new opportunities for bioimaging, in particular when long‐term monitoring is required.     

获得金纳米颗粒表面C60 SERS的一种新方法

报道了覆金滤纸和滤膜上的C60表面增强拉曼散射(SERS),增强因子达到10^5以上。分别以吡啶和CS2为溶剂媒质,对C60吡啶金胶溶液、C60(吡啶)金胶滤纸以及C60(CS2)金胶滤膜3种体系进行了SERS研究和比较。由于其避开了溶剂和金胶中水的影响,这为金纳米颗粒表面C60 SERS研究提供了一套新的思路。通过群论计算分析,并与C60固体拉曼谱相比较,得到了大量的C60分子信息。     

脉冲激光改性金属纳米薄膜的等离子体特性

在室温环境下,实验采用Nd\:YAG光纤脉冲激光器辐照银(Ag)、铜(Cu)、铝(Al)三种光滑连续的金属薄膜,制备出了对应的三种金属纳米颗粒薄膜。通过调节激光扫描速率可以实现三种金属纳米颗粒薄膜的局域表面等离子体共振(LSPR)波长和强度的调谐。其中,Ag纳米颗粒薄膜在可见光波段的等离子体吸收峰的波长和强度均表现出较宽的调谐范围,Cu纳米颗粒薄膜在可见光波段的等离子体吸收峰的波长和强度均表现较小的调谐范围,Al纳米颗粒薄膜在紫外光波段的等离子体吸收峰窄而尖锐,且LSPR波长调谐范围也较小。与激光辐照前的三种金属薄膜相比,激光辐照后生成的三种金属纳米颗粒薄膜出现了更强的表面增强拉曼散射信号。有限差分时域仿真模拟出的样品的电场强度分布与实验得到的表面增强拉曼散射结果一致。     

Ultrasonication‐Induced Self‐Assembled Fixed Nanogap Arrays of Monomeric Plasmonic Nanoparticles inside Nanopores

Monomeric gold (Au) and silver (Ag) nanoparticle (NP) arrays are self‐assembled uniformly into anodized aluminium oxide (AAO) nanopores with a high homogeneity of greater than 95%, using ultrasonication. The monomeric metal NP array exhibits asymmetric plasmonic absorption due to Fano‐like resonance as interpreted by finite‐difference time‐domain (FDTD) simulation for the numbers up to 127 AuNPs. To examine gap distance‐dependent collective‐plasmonic resonance, the different dimensions of S, M, and L arrays of the AuNP diameters/the gap distances of ≈36 nm/≈66 nm, ≈45 nm/≈56 nm, and ≈77 nm/≈12 nm, respectively, are prepared. Metal NP arrays with an invariable nanogap of ≈50 nm can provide consistent surface‐enhanced Raman scattering (SERS) intensities for Rhodamine 6G (Rh6G) with a relative standard deviation (RSD) of 3.8–5.4%. Monomeric arrays can provide an effective platform for 2D hot‐electron excitation, as evidenced by the SERS peak‐changes of 4‐nitrobenzenethiol (4‐NBT) adsorbed on AgNP arrays with a power density of ≈0.25 mW µm^‐2 at 514 and 633 nm. For practical purposes, the bacteria captured by 4‐mercaptophenylboronic acid are found to be easily destroyed under visible laser excitation at 514 nm with a power density of ≈14 mW µm^‐2 for 60 min using Ag due to efficient plasmonic‐electron transfer.     

银纳米颗粒的局域表面等离子体共振传感

采用微波法合成银纳米颗粒,通过化学自组装技术将银纳米颗粒吸附在玻璃基片上,制备了银纳米颗粒的局域表面等离子体传感器。在纯水中,紫外可见光消光谱表明局域表面等离子体共振位于428nm处。随外界折射率增加,共振峰发生红移,其折射率灵敏度达到173±6nm/RIU。在350oC温度下退火处理后,改变银颗粒在基片上的形貌,峰位发生约65nm的红移,灵敏度下降约20%。理论分析表明,银纳米颗粒形状和基底的相互作用影响折射率传感的波长响应和灵敏度特性。