基于SPR的类铬型金属膜厚在线纳米测量研究

当具有足够大发散角的柱面光照射在匀厚金属薄膜表面时,由表面等离子体振荡产生的光反射率角分布是膜厚的函数,用CCD接收反射光分布信息并经过计算机分析处理,可实时、在线测量10nm内的铬、钛等金属膜厚,这类金属的复介电常数的实部相对虚部是较小的负数,故具有强反射锐峰及较平坦的吸收峰,该两峰点可作为膜厚测量依据的特征标记点,并通过建库进行曲线匹配而获得膜厚数值。实验结果表明,该方法的平均测量误差可低于0.4nm。     

Multi-step structure of side-polished fiber sensor to enhance SPR effect

A multi-step side-polished multi-mode fiber sensor structure based on the surface plasmon resonance (SPR) and transverse magnetic (TM)-field-mode coupling phenomena is proposed. The multi-step structure with single-step, two-step, and three-step SPR fiber sensors are demonstrated via the difference in the SPR response for DI water. The time dependence of the measured intensity of transmitted light with the multi-step structure is observed as the variation increased. The structure with the advantages of no bulky components and no complicated signal processing gives an obvious SPR response and provides a two-fold increase for the sensitivity of intensity measurement.     

Molten salt synthesis and localized surface plasmon resonance study of vanadium dioxide nanopowders

Rutile-type vanadium dioxide nanopowders with four different sizes were successfully synthesized by carbothermal reducing V₂O₅ in KCl-LiCl molten salt. XRD and TEM characterizations suggested that vanadium dioxide particles formed by a broken and reunited process of vanadium oxide. Molten salt and organic carbon sources are crucial to the size of final particles. In the presence of the molten salt, the organic carbon with a shorter chain length would induce smaller particles. The UV-VIS-IR spectral measurements for as-prepared vanadium dioxide announced an obvious localized surface plasmon resonance band in the near infrared region at 90 °C.     

Surface plasmon resonance (SPR) reflectance imaging: Far-field recognition of near-field phenomena

The surface plasmon resonance (SPR) reflectance imaging technique provides a label-free visualization tool to characterize the near-field fluidic transport properties within 100 nm from the solid surface. The key idea is that the SPR reflectance intensity varies with the near-field refractive index (RI) of the test fluid, which in turn depends on the micro- and nano-fluidic scalar properties such as concentrations, temperatures, and phase changes, occurring in the near-field. As essential knowledge to understand and implement the SPR reflectance imaging technique, this paper presents discussions on the basics of surface plasmon polaritons (SPPs), surface plasmon resonance (SPR), setup of the SPR reflectance imaging system, and the SPR reflectance imaging resolution. The second part of the paper elaborates the applications of the SPR imaging sensor technique in characterizing the near-field fingerprints of nanofluidic evaporative self-assembly.     

基于狭缝扫描的表面等离子体共振成像

利用表面等离子体共振技术进行电介质样品成像研究.采用高数值孔径显微物镜作为耦合元件,632.8nm He-Ne激光会聚激发金膜产生表面等离子体共振,通过狭缝光阑限制光束入射角,对金膜上的氮化硅光栅进行成像.反射光由放置在样品像方共轭面上的CCD摄像机接收,获得样品的表面等离子体共振像.通过扫描移动狭缝,得到入射角从44°至54°的扫描样品图像,从图像中提取样品各点的表面等离子体共振曲线,由计算机重构出样品的表面等离子体共振角谱灰度图.     

Novel determination of cadmium ions using an enzyme self-assembled monolayer with surface plasmon resonance

The activity of the enzyme urease is known to be inhibited by the heavy metal cadmium. The binding of cadmium to urease and the consequent changes of the enzyme structure are the basis of the surface plasmon resonance (SPR) biosensing system reported herein. To facilitate the formation of a self-assembled monolayer (SAM) of the urease on gold-coated glass SPR sensor disks, the enzyme has been modified with N-succinimidyl 3-(2-pyridyldithiol) propionate (SPDP). The urease monolayer was exposed to trace levels of cadmium ions and monitored by SPR. From circular dichroism (CD) data, it is believed that the conformation of the active nickel site of the urease changes upon binding of the cadmium ions. It is this change of the enzyme monolayer, measured by SPR, which has been related to the cadmium ion concentration in the range of 0–10 mg l⁻¹. These data are the first report of a SPR biosensor capable of detecting metal ions.     

Surface plasmon resonance detection of oligonucleotide sequences of the rpoB genes of Mycobacterium tuberculosis

Oligonucleotide sequences related to the normal and mutated rpoB genes of Mycobacterium tuberculosis are detected using a surface plasmon resonance (SPR) biosensor system. A bioselective element was prepared by immobilizing the thiol-modified oligonucleotides of the selected sequence (the capture probe P2) that contains the mutated TCG → TTG codon 531 (evoking drug resistance) of the rpoB gene of M. tuberculosis on a gold sensor surface. Specific hybridization between immobilized probe P2 and complementary target T2 gave the highest sensor response, single-base mismatched oligonucleotide TN (corresponding to the normal gene sequence) produced somewhat smaller response and no response was observed at injection of noncomplementary oligonucleotide TC. The P2-T2 hybridization efficiency is calculated ca. 30% (5 × 10¹² molecules cm⁻²), and the lowest detection limit of T2 was 10 nM. An extended T2E oligonucleotide sequence consisting of T2 sequence and additional 24 nucleotides was shown to cause more pronounced sensor response (at least 5 nM T2E was easily detected). Injection into the sensor cell of the oligonucleotides complementary to the free additional part of T2E after P2-T2E hybridization gave a significant additional SPR response, thus showing that the sandwich hybridization format further improves the sensor sensitivity and decreases the lowest detection limit. The experimental results on surface hybridization between the studied oligonucleotides were in good agreement with thermodynamic parameters of the hybridization calculated for solution conditions. The described approach could be proposed as a basis for creating a biosensor for real-time and label-free diagnostics of drug resistant tuberculosis.     

Comparative study of sub-micrometer polymeric structures: Dot-arrays, linear and crossed gratings generated by UV laser based two-beam interference, as surfaces for SPR and AFM based bio-sensing

Two-dimensional gratings are generated on poly-carbonate films spin-coated onto thin gold-silver bimetallic layers by two-beam interference method. Sub-micrometer periodic polymer dots and stripes are produced illuminating the poly-carbonate surface by p- and s-polarized beams of a frequency quadrupled Nd:YAG laser, and crossed gratings are generated by rotating the substrates between two sequential treatments. It is shown by pulsed force mode atomic force microscopy that the mean value of the adhesion is enhanced on the dot-arrays and on the crossed gratings. The grating-coupling on the two-dimensional structures results in double peaks on the angle dependent resonance curves of the surface plasmons excited by frequency doubled Nd:YAG laser. The comparison of the resonance curves proves that a surface profile ensuring minimal undirected scattering is required to optimize the grating-coupling, in addition to the minimal modulation amplitude, and to the optimal azimuthal orientation. The secondary minima are the narrowest in presence of linear gratings on multi-layers having optimized composition, and on crossed structures consisting of appropriately oriented polymer stripes. The large coupling efficiency and adhesion result in high detection sensitivity on the crossed gratings. Bio-sensing is realized by monitoring the rotated-crossed grating-coupled surface plasmon resonance curves, and detecting the chemical heterogeneity by tapping-mode atomic force microscopy. The interaction of Amyloid-β peptide, a pathogenetic factor in Alzheimer disease, with therapeutical molecules is demonstrated.     

Toward decentralized analysis of mercury (II) in real samples. A critical review on nanotechnology-based methodologies

In recent years, it has increased the number of works focused on the development of novel nanoparticle-based sensors for mercury detection, mainly motivated by the need of low cost portable devices capable of giving fast and reliable analytical response, thus contributing to the analytical decentralization. Methodologies employing colorimetric, fluorometric, magnetic, and electrochemical output signals allowed reaching detection limits within the pM and nM ranges. Most of these developments proved their suitability in detecting and quantifying mercury (II) ions in synthetic solutions or spiked water samples. However, the state of art in these technologies is still behind the standard methods of mercury quantification, such as cold vapor atomic absorption spectrometry and inductively coupled plasma techniques, in terms of reliability and sensitivity. This is mainly because the response of nanoparticle-based sensors is highly affected by the sample matrix. The developed analytical nanosystems may fail in real samples because of the negative incidence of the ionic strength and the presence of exchangeable ligands. The aim of this review is to critically consider the recently published innovations in this area, and highlight the needs to include more realistic assays in future research in order to make these advances suitable for on-site analysis.     

帽状银纳米粒子的制备及表面增强拉曼活性研究

采用真空热蒸发法在自组装的单层阵列二氧化硅纳米粒子表面沉积银膜制备了帽状银纳米粒子。通过透射电镜(TEM)、扫描电镜(SEM)和紫外-可见-近红外分光光度计 (UV-Vis-NIR)对其表面形貌及光学性质进行了表征。以吡啶-(2-偶氮-4)间苯二酚作为探针分子，研究了该复合纳米粒子的表面增强拉曼散射 (SERS) 活性，增强因子高达2.88×10⁶。结果表明在二氧化硅纳米粒子表面制备的帽状银纳米粒子是很好的表面增强拉曼散射活性基底。