Controlled Self-Assembly of Metallacycle-Bridged Gold Nanoparticles for Surface-Enhanced Raman Scattering

In this work, well-defined two-dimensional metallacycles have been successfully employed for the well-controlled self-assembly of gold nanoparticles (AuNPs) into discrete clusters such as dimers, trimers, tetramers, pentamers and even hexamers at the water–oil interface for the first time. Furthermore, the modular construction of metallacycle molecules allows precise control of spacing between the gold nanoparticles. Interestingly, it was found that interparticle spacing below 5 nm created by molecular metallacycles in the resultant discrete gold nanoparticle clusters led to a strong plasmon coupling, thus inducing great field enhancement inside the gap between the NPs. More importantly, different discrete clusters with precise interparticle spacing provide a well-defined system for studying the hot-spot phenomenon in surface-enhanced Raman scattering (SERS); this revealed that the SERS effects were closely related to the interparticle spacing.     

Raman Enhancement of Nanoparticle Dimers Self-Assembled Using DNA Origami Nanotriangles

Surface-enhanced Raman scattering is a powerful approach to detect molecules at very low concentrations, even up to the single-molecule level. One important aspect of the materials used in such a technique is how much the signal is intensified, quantified by the enhancement factor (EF). Herein we obtained the EFs for gold nanoparticle dimers of 60 and 80 nm diameter, respectively, self-assembled using DNA origami nanotriangles. Cy5 and TAMRA were used as surface-enhanced Raman scattering (SERS) probes, which enable the observation of individual nanoparticles and dimers. EF distributions are determined at four distinct wavelengths based on the measurements of around 1000 individual dimer structures. The obtained results show that the EFs for the dimeric assemblies follow a log-normal distribution and are in the range of 10⁶ at 633 nm and that the contribution of the molecular resonance effect to the EF is around 2, also showing that the plasmonic resonance is the main source of the observed signal. To support our studies, FDTD simulations of the nanoparticle’s electromagnetic field enhancement has been carried out, as well as calculations of the resonance Raman spectra of the dyes using DFT. We observe a very close agreement between the experimental EF distribution and the simulated values.     

表面增强拉曼光谱:应用和发展

表面增强拉曼光谱技术(Surface-enhanced Raman spectroscopy,SERS)是一种具有超高灵敏度的指纹光谱技术,目前已广泛应用于表面科学、材料科学、生物医学、药物分析、食品安全、环境检测等领域,是一种极具潜力的痕量分析技术。 本文对SERS技术及相关的针尖增强拉曼光谱(Tip-enhanced Raman spectroscopy,TERS),壳层隔绝纳米粒子增强拉曼光谱(Shell-isolated nanoparticle-enhanced Raman spectroscopy,SHINERS)技术的发展及应用进行了综合评述,并探讨了其未来的研究热点及发展方向。     

相转化对均匀胶粒的形貌及团聚度的影响

金属盐溶液高温强迫水解是制备均分散胶体粒子的重要手段K’1．多年来人们致力于制备方法的研究，并对形成机理也有较系统的讨论．就。－FeZ（此胶粉的形成而言；张玉亭门和Moral，s山先后研究了0．02mol·L－’的F，CI。－HCI及FeCI。－NaH。PO。体系经100t陈化制备均匀球形和     

Tuning Optical Properties of Encapsulated Clusters of Gold Nanoparticles through Stimuli‐Triggered Controlled Aggregation

Gold nanoparticles entrapped in the hollow polymer nanocapsules undergo pH‐mediated controlled aggregation. Encapsulated clusters of nanoparticles show absorbance at higher wavelengths compared with individual nanoparticles. The size of the aggregates is controlled by the number of nanoparticles entrapped in individual nanocapsules. Such controlled aggregation may permit small biocompatible nanoparticles exhibit desirable properties for biomedical applications that are typically characteristic of large nanoparticles.     

Label‐Free Molecular Imaging of Biological Cells and Tissues by Linear and Nonlinear Raman Spectroscopic Approaches

Raman spectroscopy is an emerging technique in bioanalysis and imaging of biomaterials owing to its unique capability of generating spectroscopic fingerprints. Imaging cells and tissues by Raman microspectroscopy represents a nondestructive and label‐free approach. All components of cells or tissues contribute to the Raman signals, giving rise to complex spectral signatures. Resonance Raman scattering and surface‐enhanced Raman scattering can be used to enhance the signals and reduce the spectral complexity. Raman‐active labels can be introduced to increase specificity and multimodality. In addition, nonlinear coherent Raman scattering methods offer higher sensitivities, which enable the rapid imaging of larger sampling areas. Finally, fiber‐based imaging techniques pave the way towards in vivo applications of Raman spectroscopy. This Review summarizes the basic principles behind medical Raman imaging and its progress since 2012.     

Tuning the Colloidal Crystal Structure of Magnetic Particles by External Field

Manipulation of the self‐assembly of magnetic colloidal particles by an externally applied magnetic field paves a way toward developing novel stimuli responsive photonic structures. Using microradian X‐ray scattering technique we have investigated the different crystal structures exhibited by self‐assembly of core–shell magnetite/silica nanoparticles. An external magnetic field was employed to tune the colloidal crystallization. We find that the equilibrium structure in absence of the field is random hexagonal close‐packed (RHCP) one. External field drives the self‐assembly toward a body‐centered tetragonal (BCT) structure. Our findings are in good agreement with simulation results on the assembly of these particles.     

Plasmonic Spherical Nanoparticles Coupled with Titania Nanotube Arrays Prepared by Anodization as Substrates for Surface-Enhanced Raman Spectroscopy Applications: A Review

As surface-enhanced Raman spectroscopy (SERS) continues developing to be a powerful analytical tool for several probes, four important aspects to make it more accessible have to be addressed: low-cost, reproducibility, high sensibility, and recyclability. Titanium dioxide nanotubes (TiO₂ NTs) prepared by anodization have attracted interest in this field because they can be used as safe solid supports to deposit metal nanoparticles to build SERS substrate nanoplatforms that meet these four desired aspects. TiO₂ NTs can be easily prepared and, by varying different synthesis parameters, their dimensions and specific features of their morphology can be tuned allowing them to support metal nanoparticles of different sizes that can achieve a regular dispersion on their surface promoting high enhancement factors (EF) and reproducibility. Besides, the TiO₂ photocatalytic properties enable the substrate’s self-cleaning property for recyclability. In this review, we discuss the different methodological strategies that have been tested to achieve a high performance of the SERS substrates based on TiO₂ NTs as solid support for the three main noble metal nanoparticles mainly studied for this purpose: Ag, Au, and Pt.     

三组分抗原的磁分离及分离效率的SERS研究

利用种子生长法制备了磁性γ-Fe₂O₃@Au核壳纳米粒子, 通过修饰抗体实现表面功能化, 利用抗原抗体间的特异性作用, 通过外加磁场对三组分抗原进行了逐个以及双抗原的磁分离, 采用基于表面增强拉曼光谱(SERS)技术的免疫检测方法对磁分离效率进行了评价, 并且研究了该磁分离和效率评估方法的极限工作浓度. 研究结果表明, 该磁免疫分离法能对三组分混合抗原中的任意组分进行很好的选择性分离, 而不影响其它抗原的存在, 使其分离后溶液中被分离抗原的浓度降低到SERS免疫检测限, 分离所能达到的极限抗体浓度约0.1 pg/mL.     

Noble‐Metal‐Free Materials for Surface‐Enhanced Raman Spectroscopy Detection

Surface‐enhanced Raman spectroscopy (SERS) is an attractive tool for the sensing of molecules in the fields of chemical and biochemical analysis as it enables the sensitive detection of molecular fingerprint information even at the single‐molecule level. In addition to traditional coinage metals in SERS analysis, recent research on noble‐metal‐free materials has also yielded highly sensitive SERS activity. This Minireview presents the recent development of noble‐metal‐free materials as SERS substrates and their potential applications, especially semiconductors and emerging graphene‐based nanostructures. Rather than providing an exhaustive review of this field, possible contributions from semiconductor substrates, characteristics of graphene enhanced Raman scattering, as well as effect factors such as surface plasmon resonance, structure and defects of the nanostructures that are considered essential for SERS activity are emphasized. The intention is to illustrate, through these examples, that the promise of noble‐metal‐free materials for enhancing detection sensitivity can further fuel the development of SERS‐related applications.     

银薄层控制金纳米四足体的重塑和等离激元调谐

探究了溶液中不同温度以及不同溶液成分（I^-的引入）对金纳米四足体（GNTPs）重塑过程的影响,表明了GNTPs的重塑机制为Ostwald熟化,即弱结合的表面Au原子在高凸曲率区域溶解和在凹区域重新沉积。这种重塑过程可以随时通过镀银薄层在几秒内阻止,GNTPs的形貌可以在最大程度上得到很好的稳定,从而也可以防止其光学性质的演变。在此基础上,通过紫外可见近红外（UV-Vis-NIR）吸收光谱和基于同步辐射的小角X射线散射（SAXS）进一步研究了GNTPs/Ag的稳定性,并通过表面增强拉曼散射（SERS）光谱证实了GNTPs/Ag的光学响应。     

银薄层控制金纳米四足体的重塑和等离激元调谐

探究了溶液中不同温度以及不同溶液成分(I^-的引入)对金纳米四足体(GNTPs)重塑过程的影响，表明了GNTPs的重塑机制为Ostwald熟化，即弱结合的表面Au原子在高凸曲率区域溶解和在凹区域重新沉积。这种重塑过程可以随时通过镀银薄层在几秒内阻止，GNTPs的形貌可以在最大程度上得到很好的稳定，从而也可以防止其光学性质的演变。在此基础上，通过紫外可见近红外(UV-Vis-NIR)吸收光谱和基于同步辐射的小角X射线散射(SAXS)进一步研究了GNTPs/Ag的稳定性，并通过表面增强拉曼散射(SERS)光谱证实了GNTPs/Ag的光学响应。     

Overview of Popular Techniques of Raman Spectroscopy and Their Potential in the Study of Plant Tissues

Raman spectroscopy is one of the main analytical techniques used in optical metrology. It is a vibration, marker-free technique that provides insight into the structure and composition of tissues and cells at the molecular level. Raman spectroscopy is an outstanding material identification technique. It provides spatial information of vibrations from complex biological samples which renders it a very accurate tool for the analysis of highly complex plant tissues. Raman spectra can be used as a fingerprint tool for a very wide range of compounds. Raman spectroscopy enables all the polymers that build the cell walls of plants to be tracked simultaneously; it facilitates the analysis of both the molecular composition and the molecular structure of cell walls. Due to its high sensitivity to even minute structural changes, this method is used for comparative tests. The introduction of new and improved Raman techniques by scientists as well as the constant technological development of the apparatus has resulted in an increased importance of Raman spectroscopy in the discovery and defining of tissues and the processes taking place in them.     

Novel Silver/Poly(vinyl alcohol) Nanocomposites for Surface‐Enhanced Raman Scattering‐Active Substrates

Summary: Surface‐enhanced Raman scattering (SERS)‐active substrates with high enhancement were prepared by an in situ reduction method. Novel silver/poly(vinyl alcohol) (PVA) nanocomposite films were obtained, in which the silver nitrate, poly(γ‐glutamic acid) (PGA), and PVA acted as precursor, stabilizer, and polyol reducant, respectively. The UV‐visible spectra of the as‐fabricated films showed that the surface plasmon resonance (SPR) absorption band was narrow and of a stronger intensity, which indicates that the Ag nanoparticle size distribution on the substrate was highly uniform. This finding was further confirmed by X‐ray diffraction (XRD), transmission electron microscopy (TEM), and field‐emission scanning electron microscope (FE‐SEM) measurements. It was found that a PGA‐stabilized PVA nanocomposite film revealed the presence of well‐dispersed spherical silver nanoparticles with an average diameter of 90 nm. The new substrate presents high SERS enhancement and the enhanced factor is estimated to be 10⁶ for the detection of benzoic acid.

The Raman scattering enhancement factor for the Raman spectra of benzoic acid on the various nanocomposite films.     

离子液体中铜纳米粒子膜的电沉积制备及表面增强拉曼光谱

采用恒电位方法研究了室温离子液体1-丁基-3-甲基咪唑氟硼酸盐([BMIM]BF₄)中氧化铟锡(ITO)电极表面Cu的沉积过程. 结果表明, Cu²⁺在ITO表面经中间产物Cu⁺还原为Cu. 采用XRD和SEM对不同电位下沉积层的组成和结构进行了考察. 结果表明, 表面组成和结构与沉积电位有关. 在较正电位下沉积所得为Cu/Cu₂O的混合纳米粒子; 在较负电位下为Cu纳米粒子. 随着沉积电位逐渐变负, 其形貌经历了花状、 棒状向球形纳米粒子转变的过程, 且所得沉积膜逐渐变得致密, 其中Cu纳米粒子膜表现出较强的表面增强拉曼散射(SERS)活性, 并且SERS信号均一.     

抗癌金属络合物与脱氧核糖核酸作用的谱学研究比较

利用紫外可见光谱、荧光光谱、表面增强拉曼光谱研究了抗癌金属络合物与ＤＮＡ的相互作用,首次提出将荧光光谱与表面增强拉曼光谱结合作了化合物是否具有抗癌活性筛选法的可能性。     

Plasmonic Hotspots in Air: An Omnidirectional Three‐Dimensional Platform for Stand‐Off In‐Air SERS Sensing of Airborne Species

Molecular‐level airborne sensing is critical for early prevention of disasters, diseases, and terrorism. Currently, most 2D surface‐enhanced Raman spectroscopy (SERS) substrates used for air sensing have only one functional surface and exhibit poor SERS‐active depth. “Aerosolized plasmonic colloidosomes” (APCs) are introduced as airborne plasmonic hotspots for direct in‐air SERS measurements. APCs function as a macroscale 3D and omnidirectional plasmonic cloud that receives laser irradiation and emits signals in all directions. Importantly, it brings about an effective plasmonic hotspot in a length scale of approximately 2.3 cm, which affords 100‐fold higher tolerance to laser misalignment along the z‐axis compared with 2D SERS substrates. APCs exhibit an extraordinary omnidirectional property and demonstrate consistent SERS performance that is independent of the laser and analyte introductory pathway. Furthermore, the first in‐air SERS detection is demonstrated in stand‐off conditions at a distance of 200 cm, highlighting the applicability of 3D omnidirectional plasmonic clouds for remote airborne sensing in threatening or inaccessible areas.     

Controlled Dispersion of Silver Nanoparticles into the Bulk of Thermosensitive Polymer Microspheres: Tunable Plasmonic Coupling by Temperature Detected by Surface Enhanced Raman Scattering

By in situ reduction of Ag⁺ ions pre‐dispersed inside thermosensitive microspheres of poly[(N‐isopropylacrylamide)‐co‐(methacrylic acid)] (P(NIPAM‐co‐MAA)), a 3D copolymer‐supported network of silver nanoparticles is created and extensively characterized by surface‐enhanced Raman scattering (SERS). The effective dispersion and the suitable density of the silver nanoparticles in the composite microspheres are demonstrated by the thermal‐induced SERS signal and its high reproducibility during thermocycling. When the temperature of the system increases above 32 °C, spatial separation of the silver nanoparticles decreases and the numbers of Ag nanoparticles and P(NIPAM‐co‐MAA) microspheres under illumination spot increase as a result of the shrinkage of the P(NIPAM‐co‐MAA) chains, leading to the ramp of the SERS effect. By means of the high reversibility of the thermosensitive phase transition of the P(NIPAM‐co‐MAA) microspheres, SERS activity of the silver nanoparticle network embedded in the microsphere can be well controlled by thermal‐induced variation of special separation.