银光栅/银纳米颗粒复合结构的光场增强研究

通过时域有限差分法模拟了银光栅/银纳米颗粒复合结构的消光光谱和分布于光栅槽底的银纳米颗粒周围的电场分布。光栅的周期显著影响光栅和纳米颗粒之间的耦合作用,复合结构的共振峰随周期的增加而红移;在不同激发波长下,纳米颗粒周围的电场随周期的变化呈现出不同的规律。为了考察这种复合结构在表面增强拉曼散射光谱(SERS)研究中作为基底时的增强效果,比较了复合结构在785,633,532nm激光激发下的光场增强随周期的变化规律,得到综合增强性能最优的光栅周期为520nm。为了进一步提高复合结构的光场增强效果,对光栅栅脊宽度进行了优化。在优化好光栅周期和栅脊宽度的基础上,从SERS基底化学稳定性的需求出发,仿真了在光栅表面添加4nm金膜层后的银-金光栅/银纳米颗粒复合结构的电场增强效果。     

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.     

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。     

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.     

米状银纳米颗粒对局域电场增强的理论模拟

为了提高表面增强拉曼散射技术中基底的增强效果,采用时域有限差分算法从理论上对不同入射光偏振方向下米状银纳米颗粒的电场增强进行了模拟分析,分别研究了单个银纳米颗粒和不同组合的二聚体以及三聚体的形状、间距对局域电场强度的影响,并且详细讨论了导致电场增强的原因。结果表明,当米状银纳米颗粒长度约为300 nm时,应控制其短轴约为36 nm,间距约为2 nm,且入射光偏振方向平行于长轴,此时在颗粒的尖端处均会产生最大电场增强,其中二聚体尖端对尖端情形下增强效果尤为明显。该结论为拉曼基底实验中纳米颗粒的制备提供了一定的理论基础。     

利用激光诱导化学沉积法制备锥形光纤SERS探针

实验研究了激光诱导化学沉积法(LICDM)制备锥形光纤表面增强拉曼散射(SERS)探针及其SERS检测性能。结果表明,因不同角度光纤探针锥面出射光场分布不同,导致了LICDM在制备小锥角光纤探针时沉积纳米颗粒的困难,但是通过延长反应时间,利用银纳米颗粒的光散射效应可改善小角度光纤探针表面纳米颗粒的制备效果。实验利用100mW的诱导激光,在0.005mol/L反应液中,经60min沉积,制备出了不同锥角的光纤探针。对光纤探针的测试结果表明,锥角为8.2°的光纤探针所测得的SERS频移峰及其荧光背景的幅度最大,且该角度在不同SERS激发光功率下基本不变。     

基于激光诱导表面条纹微结构的着色机理

研究表面条纹微结构对激光诱导氧化膜着色机理的影响,具体分析不同工艺参数下激光诱导表面微结构的条纹宽度、条纹高度及条纹重叠度的变化特性。首先,通过改变离焦量、脉冲频率、扫描速度、条纹间隔、功率及打标次数等工艺参数来制备样本,观测并分析样本的条纹宽度受能量密度、光斑重叠度的影响,以估算条纹宽度。然后,通过条纹宽度和测量的表面粗糙度近似计算了条纹高度,理论与实际误差为-0.375～0.430μm。同时,通过条纹宽度和条纹间隔计算了条纹间重叠度,并分析条纹高度、条纹间重叠度及表面粗糙度三者之间的关系。最后,通过表面粗糙度与条纹间隔计算类光栅闪耀角,发现类光栅闪耀角能更好地描述条纹凹凸程度。多次打标样本具有颜色饱和效应,并提出一种多层颜色打标模型。     

纳米金修饰碳纳米管阵列结构的表面增强拉曼散射

研究了纳米金粒子修饰碳纳米管阵列结构的表面增强拉曼散射性能.通过FDTD理论模拟仿真了不同粒径纳米金颗粒的场强分布;并采用化学还原的方法制备出直径分别为20、40和60 nm三种不同粒径的金颗粒,然后将纳米金粒子修饰到有序定向的碳纳米管阵列表面,并将该结构作为表面增强拉曼基底.FDTD软件仿真结果表明,60 nm粒径的纳米金颗粒周围场强分布最强,是入射场场强的15倍.同时将罗丹明6G溶液用于测试几组不同尺寸的金颗粒对拉曼散射光强的影响,发现60 nm金颗粒对R6G拉曼信号增强最大.FDTD理论模拟仿真和罗丹明6G溶液实验测试结果表明:金颗粒尺寸在20～60 nm内,颗粒尺寸越大,拉曼散射光的光强越大.     

激光烧蚀法制备氧化锌纳米颗粒及其光谱特性

采用激光烧蚀法，在不同功率条件下，制备出氧化锌纳米颗粒，并对其进行了尺寸表征、光致发光和拉曼光谱测量。结果表明：在不同功率条件下获得的氧化锌纳米颗粒尺寸分布均为10～50 nm，但是随着激光烧蚀功率的增加，颗粒的凝聚程度增大，导致其光致发光谱发生红移;而其拉曼光谱不发生变化。最后，对氧化锌纳米颗粒的激光烧蚀机制进行了解释。     

Cucurbiturils-Mediated Noble Metal Nanoparticles for Applications in Sensing,SERS, Theranostics,and Catalysis

Noble metal nanoparticles (NMNPs), which spring up like mushrooms, are gaining momentum owing to their unique physicochemical characteristics. Cucurbiturils, a class of synthetic macrocycles with intriguing and peculiar host–guest properties, have stimulated tremendous research interest in recent years. The marriage of NMNPs with cucurbiturils is expected to integrate and enhance the excellent characteristics of both components, e.g., precisely controlled particle size, stability, assembly, surface functionality, biocompatibility, tunable optical properties, and high catalytic activities. This review systematically outlines the recent progress on the fabricating strategies and important applications of cucurbiturils-mediated NMNPs in sensing, surface-enhanced Raman scattering, theranostics, and catalysis. A brief outlook on the future development of cucurbiturils-mediated NMNPs is also presented.     

脉冲准分子激光制备PCLT热释电薄膜

采用脉冲激光沉积的方法,在Pt/SiO_2/Si衬底上制备了掺Ca的(Pb,La)TiO_3薄膜。薄膜呈多晶结构,具有较好的铁电性和热释电性。由于掺Ca的作用,使薄膜的材料探测优值和电压响应优值几乎与单晶MgO衬底上的c轴取向的PbTiO_3或(Ph,La)TiO_3薄膜相比拟。这些较好的实验结果是在硅基衬底上的铁电薄膜中获得的,因而对研制单片集成的红外热释电阵列将有一定的意义。     

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 nanoparticles and silver molybdate nanowires complex for surface-enhanced Raman scattering substrate

Selective synthesis of silver and uniform single crystalline silver molybdate nanowires in large scale can be easily realized by a facile soft template approach.Ag6Mo10O33 nanowires with a uniform diameter of about 50nm and the length up to several hundred micrometers were synthesized in large scale for the first time at room temperature using 12-silicotungstic acid system. The silver nanoparticles can be easily synthesized with the assistance of UV-light. Sensitive surfaceenhanced Raman scattering signals of p-aminothiophenol were observed on Ag nanoparticles and silver molybdate nanowires complex. The results demonstrated that synthetic method could be a potential mild way to selectively synthesize various molybdate nanowires with various phases in large scale. The silver nanoparticles and silver molybdate nanowires complex would be proposed for surface-enhanced Raman scattering substrate.     

Polymeric Multilayers that Contain Silver Nanoparticles can be Stamped onto Biological Tissues to Provide Antibacterial Activity

The design of polyelectrolyte multilayers (PEMs) that can be prefabricated on an elastomeric stamp and mechanically transferred onto biomedically‐relevant soft materials, including medical‐grade silicone elastomers (E’～450–1500 kPa; E’‐elastic modulus) and the dermis of cadaver skin (E’～200–600 kPa), is reported. Whereas initial attempts to stamp PEMs formed from poly(allylamine hydrochloride) and poly(acrylic acid) resulted in minimal transfer onto soft materials, we report that integration of micrometer‐sized beads into the PEMs (thicknesses of 6–160 nm) led to their quantitative transfer within 30 seconds of contact at a pressure of ～196 kPa. To demonstrate the utility of this approach, PEMs were impregnated with a range of loadings of silver‐nanoparticles and stamped onto the dermis of human cadaver skin (a wound‐simulant) that was subsequently incubated with bacterial cultures. Skin dermis stamped with PEMs that released 0.25 ± 0.01 μg cm^?2 of silver ions caused a 6 log₁₀ reduction in colony forming units of Staphylococcus epidermidis and Pseudomonas aeruginosa within 12 h. Significantly, this level of silver release is below that which is cytotoxic to NIH 3T3 mouse fibroblast cells. Overall, this study describes a general and facile approach for the functionalization of biomaterial surfaces without subjecting them to potentially deleterious processing conditions.     

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。     

基于表面增强拉曼光谱的结肠癌组织免疫分析

通过表面增强拉曼散射(SERS)标记抗体检测结肠癌组织切片上癌胚抗原(CEA)的表达,探讨SERS标记免疫检测技术用于临床分析结肠癌组织切片中蛋白质表达的可行性。采用种子生长法合成Ag壳Au核复合纳米粒子,将4-巯基苯甲酸(4-MBA)作为标记分子吸附于纳米粒子表面,制备出SERS探针;再将这种探针与CEA单克隆抗体相结合形成SERS免疫探针;最后通过SERS标记的抗体与结肠癌组织切片上相应的抗原发生特异性结合,对滴加探针的组织切片进行SERS检测和成像。结肠癌腺上皮出现很强的SERS信号,而除了少数非特异性吸附产生的信号之外,间质及正常上皮中几乎不出现SERS信号。通过SERS成像可以清晰地看到结肠癌腺上皮显示红色,表明结肠癌腺上皮高表达CEA,而间质及正常上皮几乎显示黑色和深蓝色,只有极个别点为红色,表明间质及正常上皮基本不表达CEA。研究表明,SERS标记抗体检测分析技术具有高灵敏度和高特异性,有望应用于结肠癌组织切片中蛋白质表达的分析,成为结肠癌辅助诊断的一种重要方法。     

Reproducible and Sensitive Plasmonic Sensing Platforms Based on Au-Nanoparticle-Internalized Nanodimpled Substrates

Electromagnetic enhancement effects through localized surface plasmon resonance considerably amplify the intensity of incident light when molecules are positioned in the vicinity of miniscule nanogaps. The aggregation of plasmonic nanoparticles synthesized using bottom-up methods has been extensively used to generate hot spots in solutions. These methods assist in obtaining non-periodic plasmonic signals, because the realization of uniform nanogaps through particle aggregation is difficult. Nanostructured substrates with gaps of 20–100 nm have also been fabricated using the top-down approach. However, the fabrication of smaller nanogap templates using these methods is difficult owing to high costs and low throughput. Therefore, a nanodimple array internalized with AuNPs is developed in this study to mitigate the challenges encountered in the bottom-up and top-down approaches. Precise nanogaps are generated by regularly internalizing AuNPs in the cavities of nanodimples through DNA hybridization. Simulations of the electric field distribution indicate that the incorporation of 80 nm-sized AuNPs into a curved nanodimpled Au substrate generate high-density volumetric hot spots within a detection volume, and result in a high plasmonic enhancement factor of 8.25 × 10⁷. The tremendous potential of the proposed plasmonic platform as an SERS-based biomedical diagnostic device is also verified.