基于表面增强拉曼光谱的甲萘威水溶液检测分析

以表面增强试剂OTR202和OTR103作为表面增强拉曼光谱(SERS)的活性基底,探索建立甲萘威水溶液的SERS检测方法。首先对比分析了甲萘威水溶液的普通拉曼光谱与SERS。然后分析了表面增强试剂与待测样本的加入量对甲萘威水溶液的SERS的影响。最后分析了质量浓度在0.1~15.0 mg/L范围内的甲萘威水溶液的SERS,并以1374 cm-1处的特征峰强度与甲萘威水溶液浓度进行线性回归,得到线性方程为y=414.5x+481.59,决定系数R2=0.9864。试验结果表明该研究方法对甲萘威水溶液的检测限可达到0.1 mg/L,说明以表面增强试剂OTR202和OTR103为SERS活性基底的SERS检测方法可用于水中甲萘威残留检测。     

Surface‐Enhanced Raman Scattering Using Microstructured Optical Fiber Substrates

Microstructured optical fibers (MOFs) represent a promising platform technology for fully integrated next generation surface enhanced Raman scattering (SERS) sensors and plasmonic devices. In this paper we demonstrate silver nanoparticle substrates for SERS detection within MOF templates with exceptional temporal and mechanical stability, using organometallic precursors and a high‐pressure chemical deposition technique. These 3D substrates offer significant benefits over conventional planar detection geometries, with the long electromagnetic interaction lengths of the optical guided fiber modes exciting multiple plasmon resonances along the fiber. The large Raman response detected when analyte molecules are infiltrated within the structures can be directly related to the deposition profile of the nanoparticles within the MOFs via electrical characterization.     

2D MXenes as a Promising Candidate for Surface Enhanced Raman Spectroscopy: State of the Art,Recent Trends,and Future Prospects

Surface-enhanced enhanced Raman spectroscopy (SERS) has emerged as a powerful analytical technique for ultrasensitive and label-free detection of chemical species, with numerous applications in various fields. Recently, 2D MXenes, have evoked substantial intrigue as promising substrates for SERS. Hence, a comprehensive understanding of the developments in the Raman effect and the mechanisms involved in SERS is highly crucial. The review reflects the advances, working principle, and dual mechanisms, including SERS's electromagnetic and chemical mechanisms. Noble metal nanostructures are highly prioritized as SERS substrates owing to their excellent sensitivity. However, due to certain disadvantages that they pose, metal-free SERS substrates with exceptional tunable properties are extensively researched in the current days. The combination of 2D MXenes and nanostructures can be effective in producing enhanced SERS signals. SERS performance of different MXene-based materials is emphasized. The performance of this combination is credited to their large surface-to-volume ratio, good electrical conductivity, and surface-terminated functionalities. The recent advancements in MXenes and MXenes-based heterostructures driven SERS sensing concerning the structural design of the material, its performance, and the mechanisms are studied. Finally, a detailed conclusion is provided with the challenges and future perspectives for designing 2D materials for efficient SERS sensors.     

SERS Aptatags: New Responsive Metallic Nanostructures for Heterogeneous Protein Detection by Surface Enhanced Raman Spectroscopy

We report here “aptatags,” which consist of aptamer‐modified silver nanoparticles (NPs) held together by an optical reporter. It is possible to use these materials to design a heterogeneous method for protein identification that takes advantage of the Raman signal enhancement by metallic nanostructures and the recognition capabilities of aptamers. Aptatags are formed by linking silver NPs with an organic dithiol molecule, followed by surface modification with thiolated single‐stranded DNA (ssDNA) corresponding to the sequence of the aptamer probe. The sensing surface involves a silver layer containing the thiolated capturing aptamer and mercaptohexadecanoic acid to minimize nonspecific binding. The overall process provides excellent selectivity and sensitivity. Detailed characterization of the sensing surface by SERS maps and atomic force microscopy was carried out to understand how structural features lead to signal generation.     

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.     

柔性表面增强拉曼光谱芯片制备

柔性表面增强拉曼光谱(SERS)基底具有灵活形变的特点,适合不规则曲面的原位检测,甚至可以直接进行擦拭取样的检测。对不同反射率的衬底进行仿真分析和实验测试,可以看到衬底的反射率对拉曼信号的收集有极大的影响。在波长为532 nm的光激发铝箔具有高反射率,因此选择铝箔作为衬底,采用银溶胶滴铸法制备柔性SERS芯片。实验通过控制溶剂成分,利用表面张力梯度引起向内马兰哥尼(Marangoni)流动以抑制咖啡环的产生,可以改善纳米粒子的分布均匀性。拉曼测试结果表明,SERS芯片的增强因子高达1.32×10⁸,对R6G溶液的检测限低至1×10^-11mol,同时芯片表现出良好的信号均匀性。     

人体组织拉曼光谱研究进展

介绍了拉曼光谱测量技术在人体皮肤、血液、乳腺、胃、肺等组织疾病诊断中的研究概况,同时介绍了拉曼测量新技术的发展概况,展望了它的发展前景.     

Rapid Characterization of Ultrathin Layers of Chalcogenides on SiO2/Si Substrates

There has been emerging interest in exploring single‐sheet 2D layered structures other than graphene to explore potentially interesting properties and phenomena. The preparation, isolation and rapid unambiguous characterization of large size ultrathin layers of MoS₂, GaS, and GaSe deposited onto SiO₂/Si substrates is reported. Optical color contrast is identified using reflection optical microscopy for layers with various thicknesses. The optical contrast of these thin layers is correlated with atomic force microscopy (AFM) and Raman spectroscopy to determine the exact thickness and to calculate number of the atomic layers present in the thin flakes and sheets. Collectively, optical microscopy, AFM, and Raman spectroscopy combined with Raman imaging data are analyzed to determine the thickness (and thus, the number of unit layers) of the MoS₂, GaS, and GaSe ultrathin flakes in a fast, non‐destructive, and unambiguous manner. These findings may enable experimental access to and unambiguous determination of layered chalcogenides for scientific exploration and potential technological applications.     

一种基于光纤器件的表面增强拉曼散射光谱检测系统

报道了一种基于表面增强拉曼散射(SERS)效应的结构简单、成本低的近红外拉曼光谱探测系统。该系统采用近红外半导体激光器作为激发光源。通过提高激发光源的输出背景抑制比,抑制激发光光纤传输产生的光纤拉曼信号,采用光纤型波分复用器滤除剩余激发光,利用光子计数模式的铟镓砷雪崩光电二极管作为探测器代替昂贵的近红外光电倍增管或近红外电荷耦合器件,实现了对4-胺苯并噻吩表面增强拉曼光谱的检测。该近红外光纤型检测系统具有结构简单、小型化、成本低廉以及远程检测等优势。     

Wide‐Area Strain Sensors based upon Graphene‐Polymer Composite Coatings Probed by Raman Spectroscopy

Functional graphene optical sensors are now viable due to the recent developments in hand‐held Raman spectroscopy and the chemical vapor deposition (CVD) of graphene films. Herein, the strain in graphene/poly (methyl methacrylate) sensor coatings is followed using Raman band shifts. The performance of an “ideal” mechanically‐exfoliated single crystal graphene flake is compared to a scalable CVD graphene film. The dry‐transferred mechanically exfoliated sample has no residual stresses, whereas the CVD sample is in compression following the solvent evaporation during its transfer. The behavior of the sensors under cyclic deformation shows an initial breakdown of the graphene‐polymer interface with the interface then stabilizing after several cycles. The Raman 2D band shift rates per unit strain of the exfoliated graphene are ≈35% higher than CVD graphene making the former more strain sensitive. However, for practical wide‐area applications, CVD graphene coatings are still viable candidates as a Raman system can be used to read the strain in any 5 μm diameter spot in the coating to an absolute accuracy of ≈0.01% strain and resolution of ≈27 microstrains (μs), which compares favorably to commercial photoelastic systems.     

Large‐Area Silver‐Coated Silicon Nanowire Arrays for Molecular Sensing Using Surface‐Enhanced Raman Spectroscopy

A new and facile method to prepare large‐area silver‐coated silicon nanowire arrays for surface‐enhanced Raman spectroscopy (SERS)‐based sensing is introduced. High‐quality silicon nanowire arrays are prepared by a chemical etching method and used as a template for the generation of SERS‐active silver‐coated silicon nanowire arrays. The morphologies of the silicon nanowire arrays and the type of silver‐plating solution are two key factors determining the magnitude of SERS signal enhancement and the sensitivity of detection; they are investigated in detail for the purpose of optimization. The optimized silver‐coated silicon nanowire arrays exhibit great potential for ultrasensitive molecular sensing in terms of high SERS signal enhancement ability, good stability, and reproducibility. Their further applications in rapidly detecting molecules relating to human health and safety are discussed. A 10 s data acquisition time is capable of achieving a limit of detection of approximately 4 × 10^?6 M calcium dipicolinate (CaDPA), a biomarker for anthrax. This value is 1/15 the infectious dose of spores (6 × 10^?5 M required), revealing that the optimized silver‐coated silicon nanowire arrays as SERS‐based ultrasensitive sensors are extremely suitable for detecting Bacillus anthracis spores.     

Gold Nanoparticles Sliding on Recyclable Nanohoodoos—Engineered for Surface‐Enhanced Raman Spectroscopy

Robust, macroscopically uniform, and highly sensitive substrates for surface‐enhanced Raman spectroscopy (SERS) are fabricated using wafer‐scale block copolymer lithography. The substrate consists of gold nanoparticles that can slide and aggregate on dense and recyclable alumina/silicon nanohoodoos. Hot‐spot engineering is conducted to maximize the SERS performance of the substrate. The substrate demonstrates remarkably large surface‐averaged SERS enhancements, greater than 10⁷ (>10⁸ in hot spots), with unrivalled macroscopic signal uniformity as characterized by a coefficient of variation of only 6% across 4 cm. After SERS analyses, the nanohoodoos can be recycled by complete removal of gold via a one‐step, simple, and robust wet etching process without compromising performance. After eight times of recycling, the substrate still exhibits identical SERS performance in comparison to a new substrate. The macroscopic uniformity combined with recyclability at conserved high performance is expected to contribute significantly on the overall competitivity of the substrates. These findings show that the gold nanoparticles sliding on recyclable nanohoodoo substrate is a very strong candidate for obtaining cost‐effective, high‐quality, and reliable SERS spectra, facilitating a wide and simple use of SERS for both laboratorial and commercial applications.     

Micro‐/Nanostructured Highly Crystalline Organic Semiconductor Films for Surface‐Enhanced Raman Spectroscopy Applications

The utilization of inorganic semiconductors for surface‐enhanced Raman spectroscopy (SERS) has attracted enormous interest. However, despite the technological relevance of organic semiconductors for enabling inexpensive, large‐area, and flexible devices via solution processing techniques, these π‐conjugated systems have never been investigated for SERS applications. Here for the first time, a simple and versatile approach is demonstrated for the fabrication of novel SERS platforms based on micro‐/nanostructured 2,7‐dioctyl[1]benzothieno[3,2‐b][1]benzothiophene (C8‐BTBT) thin films via an oblique‐angle vapor deposition. The morphology of C8‐BTBT thin films is manipulated by varying the deposition angle, thus achieving highly favorable 3D vertically aligned ribbon‐like micro‐/nanostructures for a 90° deposition angle. By combining C8‐BTBT semiconductor films with a nanoscopic thin Au layer, remarkable SERS responses are achieved in terms of enhancement (≈10⁸), stability (>90 d), and reproducibility (RSD < 0.14), indicating the great promise of Au/C8‐BTBT films as SERS platforms. Our results demonstrate the first example of an organic semiconductor‐based SERS platform with excellent detection characteristics, indicating that π‐conjugated organic semiconductors have a great potential for SERS applications.     

近红外激光拉曼技术在体探测胃癌腹膜播散

以腹膜接种人胃癌细胞SGC-7901的裸鼠为胃癌腹膜播散的动物模型,进行模拟外科手术,在体探测不同种植期的裸鼠腹膜癌结节及正常腹膜组织的激光拉曼光谱,对比光谱差异,采用支持向量机(SVM)算法对光谱进行分类和分期判决。结果表明,癌结节和正常组织拉曼光谱差异显著,用支持向量机算法进行分类的灵敏度、特异度和诊断准确度分别为95.73%、70.73%和90.73%;不同生长期的癌结节组织拉曼光谱也存在明显差异,用支持向量机算法进行分期的结果分别为98.82%、98.73%和98.78%。从分类结果可以看出,此方法对指导外科手术中癌变组织的识别有重要的意义。     

移频激发差分拉曼光谱仪的多波长光源设计

拉曼光谱检测常常受到荧光的干扰,影响了该技术的推广应用。移频激发差分拉曼光谱方法(SERDS方法)已被证明是一种有效的荧光抑制方法。SERDS实现荧光抑制的关键在于其特殊的激光光源,不仅要求其输出多个相近的波长,而且要求输出的激光功率较高、光谱线宽窄。采用Littrow光栅外腔半导体激光器原理设计实现了一种低成本、便携式的激光光源,可以在15nm的调谐范围内输出多个波长,光谱线宽小于0.2nm,输出功率可达80mW,适合用作移频激发差分拉曼光谱方法的多波长光源,实现拉曼光谱检测中对荧光干扰的抑制。     

In Situ Atomic Force Microscopy of the Reconfiguration of On‐Surface Self‐Assembled DNA‐Nanoparticle Superlattices

The ability to dynamically reconfigure superlattices in response to external stimuli is an intriguing prospect for programmable DNA‐guided nanoparticle (NP) assemblies, which promises the realization of “smart” materials with dynamically adjustable interparticle spacing and real‐time tunable properties. Existing in situ probes of reconfiguration processes have been limited mostly to reciprocal space methods, which can follow larger ordered ensembles but do not provide access to real‐space pathways and dynamics. Here, in situ atomic force microscopy is used to investigate DNA‐linked NP assemblies and their response to external stimuli, specifically the contraction and expansion of on‐surface self‐assembled monolayer superlattices upon reversible DNA condensation induced by ethanol. In situ microscopy allows observation and quantification of key processes in solution, e.g., lattice parameter changes, defects, and monomer displacements in small groups of NPs. The analysis of imaging data uncovers important boundary conditions due to DNA bonding of NP superlattices to a substrate. Tension in the NP–substrate DNA bonds, which can elastically extend, break, and re‐form during contraction/expansion cycles, counteracts the changes in lattice parameter and causes hysteresis in the response of the system. The results provide insight into the behavior of supported DNA‐linked NP superlattices and establish a foundation for designing and probing tunable nanocrystal‐based materials in solution.     

Highly Intensified Surface Enhanced Raman Scattering by Using Monolayer Graphene as the Nanospacer of Metal Film–Metal Nanoparticle Coupling System

It is widely accepted that surface enhanced Raman scattering (SERS) enhancement results from a combination of electromagnetic mechanisms (EM) and chemical mechanisms (CM). Recently, the nanoparticle‐film gap (NFG) system was studied due to its strong local enhancement field. However, there are still some technical limitations in establishing effective and simple ways for reliable and precise control of sub‐nanospacer. In addition, works on designing the nanospacer in NFG system for efficient interaction with target molecules for further improving SERS signals are rather limited. Here, a novel NFG system is proposed by introducing ultrathin monolayer graphene as well‐defined sub‐nanospacer between Ag NPs and Ag film (named G(graphene)‐NFG system). The new G–NFG system offers tremendous near‐field enhancement with one of the highest enhancement ratio of 1700 reported to date. These results show that the single‐layer graphene as a sub‐nanospacer renders the proposed G–NFG system with particularly strong EM enhancement (due to multiple couplings including the NP–NP couplings and NP‐film couplings) and additional CM enhancement in detecting some π‐conjugated molecules to function as a powerful tool in analytical science and the related fields.     

拉曼光谱技术在深海原位探测中的研究进展

拉曼光谱是一种分子指纹光谱,在物质成分识别和定量分析领域已得到广泛应用,近年来也逐渐应用于深海极端环境 的原位探测。回顾了激光拉曼光谱技术的发展历程,介绍了国内外已经研发的深海激光拉曼光谱探测系统,并着重介绍 了各系统在深海冷泉、热液等极端区域对喷口流体、沉积物孔隙水、自生碳酸盐岩、水合物等目标物的原位探测和 应用,最后总结了限制拉曼光谱技术在深海取得更多应用的因素,可以为拉曼光谱技术未来的发展提供参考。     

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.