Plasmonic films based on colloidal lithography

This paper reviews recent advances in the field of plasmonic films fabricated by colloidal lithography. Compared with conventional lithography techniques such as electron beam lithography and focused ion beam lithography, the unconventional colloidal lithography technique with advantages of low-cost and high-throughput has made the fabrication process more efficient, and moreover brought out novel films that show remarkable surface plasmon features. These plasmonic films include those with nanohole arrays, nanovoid arrays and nanoshell arrays with precisely controlled shapes, sizes, and spacing. Based on these novel nanostructures, optical and sensing performances can be greatly enhanced. The introduction of colloidal lithography provides not only efficient fabrication processes but also plasmonic films with unique nanostructures, which are difficult to be fabricated by conventional lithography techniques.     

Plasmonic heterogeneous catalysis for organic transformations

Plasmonic catalysis has been recognised as a promising alternative to many conventional thermal catalytic processes in organic synthesis. In addition to their high activity in fine chemical synthesis, plasmonic photocatalysts are also able to maintain control of selectivity under mild conditions by utilising visible-light as an energy source. This review provides an overview of the recent advances in organic transformations with plasmonic metal nanostructures, including selective reduction, selective oxidation, cross-coupling and addition reactions. We also summarize the photocatalysts and catalytic mechanisms involving surface plasmon resonance. Finally, control of reaction pathway and strategies for tailoring product selectivity in fine chemical synthesis are discussed.     

表面等离激元金属纳米粒子的多元化结构及应用

目前, 单一的金属纳米粒子结构已经难以满足多学科交叉发展的需求. 因此, 将多种金属纳米粒子(如不同尺寸、 形状、 组分等)集成在同一基底表面, 能够充分发挥不同金属纳米粒子的性质和优势, 极具研究价值和应用价值. 本文介绍了多元化表面等离激元纳米粒子结构的构筑方法, 以及其在信息编码、 光电器件、 能源催化等领域的应用. 最后, 提出了当前在多元化结构制备中存在的挑战, 并展望了利用多元化结构实现性能提升的前景.     

可调控且稳定的SrMoO4等离激元共振用于增强的可见光驱动的氮还原

光催化固氮是最具潜力的人工光合过程之一,也是有望取代工业Haber-Bosch方法实现氨的绿色合成的清洁能源技术之一.由于氮气分子还原为氨需要较高的还原电位,导致大部分常规的半导体材料的导带能级不能满足固氮反应的热力学要求.同时,固氮光催化剂普遍存在光响应波段窄、表面催化活性低、太阳光向氨的转化效率低等问题.缺陷工程是目前制备高效固氮光催化剂的最有效的途径之一.在催化剂中引入缺陷可以带来两个方面的好处:(1)促进氮气分子在缺陷位点上的化学吸附和活化,从而降低反应能垒;(2)拓宽催化剂的太阳光响应波段,提高对太阳光的利用效率.等离激元效应来自于自由载流子的集体振荡,广泛存在于金属纳米结构中.尽管金属等离激元纳米材料在光催化中也有广泛的应用,可以通过等离激元增强的光吸收和散射、热载流子传输以及等离激元共振能量传递等机理提高太阳能转化效率,但其能量转化效率仍有限,多用于弥补半导体材料的弱点.研究发现,一些半导体纳米材料在可见光和近红外光范围表现出优异的等离激元共振吸收.相比等离激元金属纳米材料,这些半导体的等离激元共振效应的调控手段更加丰富.等离激元半导体材料普遍具有较高的缺陷浓度、非常宽的光响应波段,因而是理想的固氮光催化剂.本文利用具有还原性的气氛处理溶剂热法制备的SrMoO4,通过引入高浓度的氧空位,实现了可调控的稳定的等离激元共振吸收.制备的SrMoO4在可见光和近红外光范围具有强的等离激元吸收,其共振吸收峰的中心位置可从520调到815 nm,显著拓宽了SrMoO4的光响应波段,而样品的本征吸收边仍然位于310 nm.研究发现,氢气还原没有改变Sr的氧化态,而是将Mo6+还原成Mo5+.紫外光电子能谱分析结果表明,高温氢气处理没有改变SrMoO4样品的导带和价带能级.电子顺磁共振研究结果表明,氢气处理在SrMoO4中形成了大量的氧空位.Mott-Schottky测试结果发现,氢气处理后的样品的载流子浓度高达～2.0×1020 cm-3.具有等离激元效应的SrMoO4表现出优异的可见光固氮性能,相比不具有等离激元效应的SrMoO4,在入射光波长大于420 nm的可见光照射下,在氢气气氛中处理10 min,3,6和8h的SrMoO4样品的氨的产率分别为41.2,36.3,24.5和20.8 μg gcat-1 h-1.其增强光催化活性主要来源于更宽的太阳光吸收波段、等离激元激发产生的热载流子和丰富的缺陷活性位点.一方面,SrMoO4具有较高的导带能级,本征激发形成的导带电子能在热力学上将氮气分子还原为氨;另一方面,等离激元激发产生的热载流子具有较高的能量,能够越过固液界面的肖特基能垒,将吸附在催化剂表面缺陷处的氮气分子还原为氨.但是,尽管缺陷在光催化固氮中展现出多方面的优点,其在半导体中的浓度仍需进一步的优化.     

Highly sensitive colorimetric detection of NH3 based on Au@Ag@AgCl core-shell nanoparticles

As an important component of the atmosphere, ammonia (NH₃) plays a very important role in maintaining the balance of environment. However, it is also one of the most toxic gases that can cause damage to the human respiratory system and mucous membranes even at low concentrations. As such, development of highly sensitive and selective NH₃ sensors is of high significance for environmental monitoring and health maintenance. Herein, we have synthesized Au@Ag@AgCl core-shell nanoparticles (NPs) by oxidative etching and precipitating Au@Ag core-shell NPs using FeCl₃ and further used them as optical probes for the colorimetric detection of NH₃. The sensing mechanism is based on the fact that the etching of NH₃ on AgCl and Ag shell leads to the variations of ingredients and core-to-shell ratio of the Au@Ag@AgCl NPs, thereby inducing noticeable spectral and color changes. By replacing the outmost layer of Ag with AgCl, not only is the stability of the sensor against oxygen significantly enhanced, but also is the sensitivity of the method improved. The method exhibits good linear relationship for the detection of NH₃ from 0 to 5000 μmol/L with the limit of detection of 6.4 μmol/L. This method was successfully applied to the detection of simulated air polluted by NH₃, indicating its practical applicability for environmental monitoring. This method shows great potential for on-site NH₃ detection particularly in remote area, where a simple, fast, low-cost, and easy-to-handle method is highly desirable.     

Optical DNA detection based on gold nanorods aggregation

Sequence-specific DNA detection is important in various biomedical applications such as gene expression profiling, disease diagnosis and treatment, drug discovery and forensic analysis. Herein, the localized surface plasmon resonance properties of unmodified gold nanorods (GNRs) in 1 mM cetyltrimethyl-ammonium bromide solution were used for sensing DNA sequences, with good simplicity and sensitivity. The intensity of typical plasmon resonance absorption bands of the GNRs decreased with increasing cDNA concentration. The detection of a 30-mer single-stranded oligonucleotide as a model reached a detection limit of about 0.1 pM. This study will be significant for as-prepared GNRs for future application in biological systems.     

三角银纳米柱的研究进展*

由于三角银纳米柱独特可调的光学性质及其在生物分子和无机离子检测等领域的重要应用前景而引起了人们的关注。本文综述了三角银纳米柱的研究进展,介绍了三角银纳米柱的光学性质,几种主要的制备方法,三角银纳米柱的表面修饰、颗粒膜的制备以及在无机离子检测中的应用,并对三角银纳米柱在应用中存在的结构不稳定性问题以及现行的解决方法进行了综述。     

Large‐Sized Fabrication of Tunable Plasmonic Electrodes Via Electrodeposition

Electrodeposition method, a simple, cheap, and flexible approach, to fabricate gold nanoparticle (Au NPs) films with an area larger than 1 cm² on indium tin oxide (ITO) electrodes modified with (3‐mercaptopropyl) trimethoxysilane (MPTMS) was presented. Size‐controllable and high loading Au NPs were obtained, which were characterized by field‐emission scanning electron microscopic (FESEM) and UV‐vis spectroscopy. Our current method provides a versatile and facile pathway to fabricate large‐scale metal nanoparticles thin film, enhancing alternatives for academic investigation and industrial application.     

Gas-Phase Deposited Plasmonic Nanoparticles Supported on 3D-Graphene/Nickel Foam for Highly SERS Detection

In this work, we proposed a novel three-dimensional (3D) plasmonic nanostructure based on porous graphene/nickel foam (GNF) and gas-phase deposited Ag nanoparticles (NPs).Ag NPs with high density were directly deposited on the surface of 3D GNF by performing a novel cluster beam deposition approach. In comparison with traditional Ag substrate(SiO₂/Ag), such hot-spots enriched 3D nanostructure showed extremely high electromag-netic field enhancement under incident light irradiation which could be used as a sensitive chemical sensor based on surface enhanced Raman scattering (SERS). The experimental results demonstrated that the proposed nanostructure showed superior SERS performance in terms of Raman signal reproducibility and sensitivity for the probe molecules. 3D full-wave simulation showed that the enhanced SERS performance in this 3D hierarchical plasmonic nanostructure was mainly obtained from the hot-spots between Ag NPs and the near-field coupling between Ag NPs and GNF sca olds. This work can provide a novel assembled SERS substrate as a SERS-based chemical sensor in practical applications.     

Isotope Effects in Plasmonic Photosynthesis

The photoexcitation of plasmonic nanoparticles has been shown to drive multistep, multicarrier transformations, such as the conversion of CO₂ into hydrocarbons. But for such plasmon-driven chemistry to be precisely understood and modeled, the critical photoinitiation step in the reaction cascade must be identified. We meet this goal by measuring H/D and ¹²C/¹³C kinetic isotope effects (KIEs) in plasmonic photosynthesis. In particular, we found that the substitution of H₂O with D₂O slows hydrocarbon production by a factor of 5–8. This primary H/D KIE leads to the inference that hole-driven scission of the O−H bond in H₂O is a critical, limiting step in plasmonic photosynthesis. This study advances mechanistic understanding of light-driven chemical reactions on plasmonic nanoparticles.     

Gold Nanoparticles as a Biosensor for Cancer Biomarker Determination

Molecular biology applications based on gold nanotechnology have revolutionary impacts, especially in diagnosing and treating molecular and cellular levels. The combination of plasmonic resonance, biochemistry, and optoelectronic engineering has increased the detection of molecules and the possibility of atoms. These advantages have brought medical research to the cellular level for application potential. Many research groups are working towards this. The superior analytical properties of gold nanoparticles can not only be used as an effective drug screening instrument for gene sequencing in new drug development but also as an essential tool for detecting physiological functions, such as blood glucose, antigen-antibody analysis, etc. The review introduces the principles of biomedical sensing systems, the principles of nanomaterial analysis applied to biomedicine at home and abroad, and the chemical surface modification of various gold nanoparticles.     

Molecular-level Manipulation of Interface Charge Transfer on Plasmonic Metal/MOF Heterostructures

Plasmon-excited hot carriers have drawn great attention for driving various chemical reactions, but the short lifetimes of hot carriers seriously restrict the performance of plasmonic photocatalysis. Constructing plasmonic metal/metal-organic framework (MOF) heterostructures has been proved as an effective strategy to extend the lifetimes of hot carriers. Due to the high molecular tunability of MOFs, the MOF substrate in plasmonic metal/MOF heterostructures is able to capture hot electrons on the conduction band of MOF and hot holes on its valence band, and thus offers an ideal platform to separately study the detailed mechanism of hot electron and hole transfer processes. This review focuses on a molecular-level understanding of both hot-electron and hot-hole transfer at plasmonic metal/MOF interfaces. The enhanced stability and photocatalytic performance by introducing MOF substrates are discussed for plasmonic metal/MOF heterostructures. Additionally, typical characterization technologies are also proposed as powerful tools for tracking hot carrier transfer process.     

Colloidal-based localized surface plasmon resonance (LSPR) biosensor for the quantitative determination of stanozolol

This work reports the systematic preparation of biosensors through the use of functionalized glass substrates, noble metal gold colloid, and measurement by localized surface plasmon resonance (LSPR). Glass substrate was modified through chemical silanization, and the density of gold colloid was carefully controlled by optimizing the conditions of silanization through the use of mixed silanes and selective mixing procedures. At this point, samples were exposed to bioreagents and changes in the shallow dielectric constant around the particles were observed by dark-field spectroscopy. Biological binding of high affinity systems (biotin/streptavidin and antigen/antibody) was subsequently investigated by optimizing coating layers, receptor concentration profiling, and finally quantitative determination of the analyte of interest, which in this case was a small organic molecule—the widely used, synthetic anabolic steroid called stanozolol. For this system, high specificity was achieved (>97%) through extensive nonspecific binding tests, with a sensitivity measurable to a level below the minimum required performance level (MRPL) as determined by standard chromatographic methods. Analytical best-fit parameters of Hillslope and regression coefficient are also commented on for the final LSPR biosensor. The LSPR biosensor showed good reproducibility (<5% RSD) and allowed for rapid preparation of calibration curves and determination of the analyte (measurement time of each sample ca. 2 min). As an alternative method for quantitative steroidal analysis, this approach significantly simplifies the detection setup while reducing the cost of analysis. In addition the system maintains comparable sensitivity to standard surface plasmon resonance methods and offers great potential for miniaturization and development of multiplexed devices. Figure Schematic of sensor configuration indicating both min and max controls and associatedexample localized resonance curves Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

纳米柱表面等离子体共振的调制及其红外光谱增强特性研究

采用电子束直写光刻和离子束刻蚀的方法, 将具有不同周期的纳米金柱阵列制备于透明的石英衬底上. 通过对样品的透射光谱进行采集和分析可知, 改变纳米柱阵列周期可以实现在红外波段对局域表面等离子共振的精密调节. 实验结果表明, 在透射谱中共振谷的波长随着周期的增大而红移, 且红移的距离可以通过控制纳米柱阵列的周期进行调制. 理论模拟结果与实验结果在一定程度上相吻合. 此外, 还对不同高度的纳米柱阵列的透射谱进行比较和分析. 更进一步, 将制备的纳米银柱阵列和傅里叶变换光谱仪的ATR附件相耦合, 有效增强了葡萄糖溶液的吸收谱强度. 可见周期结构的纳米柱阵列可以有效增大样品表面的近场场强, 在信号传感和检测等领域有着广泛的应用前景.     

Binding of Ricinus communis agglutinin to a galactose-carrying polymer brush on a colloidal gold monolayer

A polymer with many pendent galactose residues was prepared by atom-transfer radical polymerization (ATRP) of galactose-carrying vinyl monomer, 2-lactobionamidoethyl methacrylate (LAMA), with a disulfide-carrying ATRP initiator, 2-(2'-bromoisobutyroyl)ethyl disulfide (DT-Br). The galactose-carrying polymer obtained (DT-PLAMA) was accumulated as a polymer brush via Au-S bond on a colloidal gold monolayer deposited on a cover glass. For comparison, a disulfide which carried one galactose residue at both ends (2-lactobionamidoethyl disulfide, Cys-Lac) was accumulated as a self-assembled monolayer (SAM) on the colloidal gold monolayer, too. The association and dissociation processes of galactose residues on the colloidal gold with a lectin, Ricinus communis agglutinin (RCA(120)), were observed by the increase and decrease in absorbance at 550nm corresponding to localized surface plasmon resonance (LSPR) phenomena. The Cys-Lac SAM-carrying glass chip showed a strong non-specific adsorption of the lectin, whereas the DT-PLAMA brush-carrying one reversibly associated with the lectin, indicating reusability of the latter device. The apparent association constant of the lectin with the galactose residues in the DT-PLAMA brush was much larger than the association constant for free galactose, and the detection limit of RCA(120) by the glycopolymer brush-modified device was satisfactorily low. Furthermore, a microscopic observation clearly indicated that the DT-PLAMA brush could reversibly associate with a HepG2 cell having galactose receptors, though these processes could not be observed spectrophotometrically due to a gigantic size of the cell.     

Assembly process of CuHCF/MPA multilayers on gold nanoparticles modified electrode and characterization by electrochemical SPR

Gold nanoparticles were deposited onto 2-mercaptoethylamine (MEA)-assembled planar gold thin film to construct gold nanoparticles modified electrode by virtue of a solution-based self-assembly strategy. Subsequently, 3-mercaptopropionic acid (MPA)-bridged copper hexacyanoferrate (CuHCF) multilayers were constructed on the as-prepared gold nanoparticles modified electrode. The resulted multilayer nanostructures were investigated by electrochemical surface plasmon resonance (EC-SPR) and atomic force microscopy (AFM) with primary emphasis upon the effect of the gold nanoparticles on the MPA/CuHCF multilayers growth and their surface morphology. Compared with the multilayer system on a planar gold electrode, the different electrochemical and optical properties might result from higher curvature effect and extraordinary surface-to-volume ratio characteristic of gold nanoparticles and the nanoparticle-selective growth of CuHCF. A dendrimer-like assembly process was proposed to explain the experiment results. This new motif of multilayer on the gold nanoparticles modified electrode was different from that of on a planar gold electrode, indicating a potential application of EC-SPR technique in the study of nanocomposite materials.     

Theoretical Design and Experimental Realization of Quasi Single Electron Enhancement in Plasmonic Catalysis

By a combination of theoretical and experimental design, we probed the effect of a quasi‐single electron on the surface plasmon resonance (SPR)‐mediated catalytic activities of Ag nanoparticles. Specifically, we started by theoretically investigating how the E‐field distribution around the surface of a Ag nanosphere was influenced by static electric field induced by one, two, or three extra fixed electrons embedded in graphene oxide (GO) next to the Ag nanosphere. We found that the presence of the extra electron(s) changed the E‐field distributions and led to higher electric field intensities. Then, we experimentally observed that a quasi‐single electron trapped at the interface between GO and Ag NPs in Ag NPs supported on graphene oxide (GO‐Ag NPs) led to higher catalytic activities as compared to Ag and GO‐Ag NPs without electrons trapped at the interface, representing the first observation of catalytic enhancement promoted by a quasi‐single electron.