surface enhanced Raman spectroscopy

表面增强拉曼光谱
  • 文章类型: Journal Article
    表面增强拉曼光谱(SERS)技术是一种能够获得分析物指纹信息的有效分析技术,可以在单分子水平上提供检测极限性能,和分析在单个步骤中执行,没有任何中间步骤。SERS技术提供了额外的好处,而不是其他分析技术,包括高选择性,超灵敏检测,简单的协议,就地取样,投入能力和成本效益。由于材料和纳米技术科学的发展与SERS分析技术相结合,这项技术日益增强其使用优势。限制该技术使用的最重要因素是将含有所需分析物的溶液滴到SERS基底上,并且在随后的分析中不能再使用相同的基底。为了解决这个问题,近年来,科学家们一直致力于开发可重复使用的SERS基板。在这些研究中,科学家基本上使用了三种SERS基底清洁应用(1)用合适的溶剂洗涤SERS基底,该溶剂可以在分析后从SERS表面洗脱分析物,(2)在分析之后通过用催化活性材料对分析物进行改性,用分析物的催化降解来清洁SERS基底,和(3)在分析之后对SERS基底应用等离子体清洁程序,和(4)在SERS分析之前应用吸附和解吸程序。在这里,这篇评论文章的目的是根据其开发水平和回收潜力来评估可重复使用的SERS基底方法。这篇综述提供了关于制造SERS基板所采用的各种感测方案的连贯讨论。我们采用了一种关键方法,其中选择了详尽的示例来突出各种实验配置的关键缺点。同样,讨论了有关关键仪器进步的优点和局限性,以及该领域开发的最新方法的扩展。
    Surface Enhanced Raman Spectroscopy (SERS) technique is an effective analytical technique in which fingerprint information about analytes can be obtained, can provide detection limit performance at the single molecule level, and analyzes are performed in a single step without any intermediate steps. SERS technique offers additional benefits rather than other analytical techniques including high selectivity, ultrasensitive detection, uncomplicated protocols, in situ sampling, on-set capability and cost-effectiveness. As a result of the combination of developments in materials and nanotechnology science with the SERS analysis technique, this technique strengthens its use advantage day by day. The most important factor that limited the use of this technique was the fact that the solution containing the desired analyte(s) was dropped onto the SERS substrate and the same substrate could not be reused in subsequent analyses. To solve this problem, scientists have focused on developing reusable SERS substrates in recent years. In these studies, scientists basically used three SERS substrate cleaning applications (1) washing the SERS substrate with a suitable solvent that can elute the analyte from SERS surface after analysis, (2) cleaning the SERS substrate with catalytic degradation of analytes after analysis by modifying them with catalytic active materials and (3) Applying plasma cleaning procedure to SERS substrate after analysis and (4) applying adsorption and desorption procedure prior to SERS analysis. Herein, the aim of this review article is to evaluate the reusable SERS substrates-based methods based on their level of development and their potential to recycle. This review offers a coherent discussion on a wide range of sensing schemes employed in fabricating the SERS substrates. We utilized a critical approach in which elaborative examples were selected to highlight key shortcomings of various experimental configurations. In the same vein, there is a discussion of the advantages and limitations concerning the key instrumental advances and the expansion of the recent methods developed in this area.
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  • 文章类型: Journal Article
    二维层状半导体材料作为一类独特的材料,由于带隙窄,被广泛探索,可控形态,和可调的金属阳离子组成。在这里,我们通过结合镍钴层状双氢氧化物(NiCo-LDH)微海胆和等离子体银纳米颗粒(AgNPs)构建了表面增强拉曼光谱(SERS)传感平台,用于噻菌灵(TBZ)的杀菌剂检测。NiCo-LDHs/Ag-NP微复合材料由NiCo-LDHs微胆组成,该微胆具有大量沉积有光还原AgNP的纳米针。具有NiCo-LDHs/Ag-NP的SERS平台在TBZ检测方面表现出优异的SERS性能,包括1.49×10-11M的超低检测限,1.71×109的崇高增强因子,高均匀性,重现性好,和长期储存稳定性。NiCo-LDH/Ag-NP的超高SERS活性可归因于AgNP之间纳米级间隙中的强电磁增强,通过大面积NiCo-LDH/Ag-NP界面的大量电荷转移,以及电磁和电荷转移机制的协同作用。此外,NiCo-LDHs/Ag-NP微复合材料的独特形态为TBZ分子的吸附提供了广阔的表面积,以进一步增强拉曼信号。通过检测苹果汁和河水的实际样品中的TBZ,证实了所提出的SERS平台的实用性。即使在第五个降解周期之后,NiCo-LDHs/Ag-NP微复合材料的出色自清洁能力仍具有81.97%的保留率,这突显了其令人印象深刻的可持续可重用性和成本效益。这项工作的发现为开发高性能SERS平台以确保食品安全和环境保护奠定了基础。
    Two-dimensional layered semiconductor materials as a distinctive class of materials are comprehensively explored for widespread applications due to narrow bandgap, controllable morphology, and tunable metal cation composition. Herein, we constructed a sensing platform of surface enhanced Raman spectroscopy (SERS) by combination of nickel‑cobalt layered double hydroxide (NiCo-LDH) microurchins and plasmonic silver nanoparticles (Ag NPs) for fungicide detection of thiabendazole (TBZ). The NiCo-LDHs/Ag-NPs microcomposites consist of NiCo-LDHs microurchins having a large number of nanoneedles deposited with photoreduced Ag NPs. The SERS platform with NiCo-LDHs/Ag-NPs shows an excellent SERS performance for TBZ detection, including an ultra-low detection limit of 1.49 × 10-11 M, a sublime enhancement factor of 1.71 × 109, high uniformity, good reproducibility, and long-term storage stability. The ultrahigh SERS activity of NiCo-LDH/Ag-NPs can be attributed to strong electromagnetic enhancement in the nanoscale gaps between Ag NPs, massive charge transfer through large-area NiCo-LDH/Ag-NPs interfaces, and the synergistic action of electromagnetic and charge transfer mechanisms. Besides, the unique morphology of NiCo-LDHs/Ag-NPs microcomposite provides a broad surface area for adsorption of TBZ molecules for further Raman signal enhancement. The practicability of the proposed SERS platform is confirmed by detecting TBZ in the real samples of apple juice and river water. The exceptional self-cleaning capability of the NiCo-LDHs/Ag-NPs microcomposite with an retention rate of 81.97 % even after the fifth degradation cycle underscores its impressive sustainable reusability and cost-effectiveness. The findings in this work lay the foundation for the development of high-performance SERS platforms to ensure food safety and environmental protection.
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  • 文章类型: Journal Article
    17β-E2用于动物生长调节和农业肥料,甚至ngL-1质量浓度水平也能显示出生物学效应。在这项工作中,将AgNPs用作表面增强拉曼光谱(SERS)源,并通过简单的方法合成WS2,为AgNPs提供均匀分布平台。MIP是外壳,可以选择性地富集目标分子,拉靶分子和SERS源之间的距离,并保护AgNPs。构建了具有高灵敏度的可循环SERS底物,用于检测食品中的17β-E2。优化的WS2/Ag@MIP作为SERS基底具有高增强因子(EF=2.78×109)的优点,低检测限(LOD=0。0958pM),抗干扰能力强,和良好的回收性能。此外,实际样品中17β-E2的检测仍具有较好的准确性。本研究为食品中17β-E2的痕量检测提供了新的可能。
    17β-E2 is used in animal growth regulation and agricultural fertilizer, and even ng L-1 mass concentration levels can show biological effects. In this work, Ag NPs was used as surface-enhanced Raman spectroscopy (SERS) source and WS2 was synthesized by a simple method to provide a uniform distribution platform for Ag NPs. The MIP was the shell, which can selectively enrich the target molecule, pull the distance between the target molecule and SERS source, and protect Ag NPs. A cyclable SERS substrate with high sensitivity for detecting 17β-E2 in food was constructed. The optimized WS2/Ag@MIP as SERS substrate has the advantages of high Enhanced Factor (EF = 2.78 × 109), low detection limit (LOD = 0. 0958 pM), strong anti-interference ability, and good recycling performance. Moreover, the detection of 17β-E2 in real samples still has good accuracy. This work provides a new possibility for the trace detection of 17β-E2 in food.
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  • 文章类型: Journal Article
    根据许多国家的规定,食品和药物制剂中的大肠杆菌污染需要严格控制。然而,快速、灵敏的大肠杆菌检测仍然是一个挑战。在这项研究中,开发了一种基于适体的表面增强拉曼光谱(SERS)夹心方法,用于使用适体功能化的Au-Ag@Si三角金字塔(TP)底物快速灵敏地检测大肠杆菌。用大肠杆菌适体将Au-Ag@SiTP底物官能化,以通过与拉曼报道分子(6-羧基-X-罗丹明)整合作为捕获探针和SERS标签。捕获探针的制作,SH-apt@Au-Ag@SiTP,简单快速(20.5小时)。该方法能在约3h内选择性快速检测大肠杆菌,检出限为2.8CFU/mL。新皇片,回收率为90.19%至104.17%。结果表明,该方法简便、快速,它可能是一种有前途的替代方法,用于现场检测药物和食品样品中的大肠杆菌。
    Escherichia coli contamination in food and pharmaceutical preparations needs to be strictly controlled according to the regulations in many countries. However, rapid and sensitive E. coli detection is still a challenge. In this study, an aptamer-based surface-enhanced Raman spectroscopy (SERS) sandwich method was developed for the rapid and sensitive detection of E. coli using an aptamer-functionalized Au-Ag@Si triangular pyramid (TP) substrate. The Au-Ag@Si TP substrate was functionalized with E. coli aptamer to work as both the capture probe and SERS tag by integrating with Raman reporter (6-carboxy-X-rhodamine). The fabrication of the capture probe, SH-apt@Au-Ag@Si TP, was simple and rapid (20.5 h). This method could selectively and rapidly detect E. coli with a limit of detection of 2.8 CFU/mL within approximately 3 h. It was successfully applied to a traditional Chinese medicine preparation, Xinhuang tablets, with recoveries ranging from 90.19 % to 104.17 %. The results indicated that the developed method was simple and rapid, and it could be a promising alternative for the on-site detection of E. coli in pharmaceutical and food samples.
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  • 文章类型: Journal Article
    鼻咽癌(NPC)是一种在东南亚地区患病率高,具有高侵袭性和转移性特征的恶性肿瘤。放射治疗是鼻咽癌治疗的主要策略,然而,仍然缺乏预测治疗失败的主要原因辐射抗性的效果方法。在这里,放疗敏感和耐药组和健康组的鼻咽癌患者血浆的分子谱,分别,首次采用基于表面等离子体共振的无标记表面增强拉曼光谱(SERS)进行了研究。尤其是,通过分离过程分析了不同分子量大小的组分,有助于避免由于竞争性吸附而可能丢失的诊断信息。在此之后,采用基于主成分分析和线性判别分析的鲁棒机器学习算法(PCA-LDA)对血液SERS数据进行特征提取,建立了有效的预测模型,准确率达96.7%,100%用于识别健康的NPC受试者。这项工作证明了分子分离辅助无标记SERS结合机器学习在临床场景中用于NPC筛查和治疗策略指导的潜力。
    Nasopharyngeal cancer (NPC) is a malignant tumor with high prevalence in Southeast Asia and highly invasive and metastatic characteristics. Radiotherapy is the primary strategy for NPC treatment, however there is still lack of effect method for predicting the radioresistance that is the main reason for treatment failure. Herein, the molecular profiles of patient plasma from NPC with radiotherapy sensitivity and resistance groups as well as healthy group, respectively, were explored by label-free surface enhanced Raman spectroscopy (SERS) based on surface plasmon resonance for the first time. Especially, the components with different molecular weight sizes were analyzed via the separation process, helping to avoid the possible missing of diagnostic information due to the competitive adsorption. Following that, robust machine learning algorithm based on principal component analysis and linear discriminant analysis (PCA-LDA) was employed to extract the feature of blood-SERS data and establish an effective predictive model with the accuracy of 96.7% for identifying the radiotherapy resistance subjects from sensitivity ones, and 100% for identifying the NPC subjects from healthy ones. This work demonstrates the potential of molecular separation-assisted label-free SERS combined with machine learning for NPC screening and treatment strategy guidance in clinical scenario.
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  • 文章类型: Journal Article
    虽然广泛的研究集中在了解聚乙酸乙烯酯(PVAC)涂料在不同环境条件下的降解机理,对PVAC基白胶的长期稳定性关注有限,尤其是在艺术品中使用时。这项研究调查了加速降解,在模拟光老化下,以及对商业PVAC基白胶的等温处理,这些白胶被认为是当代艺术品中使用的此类材料的代表,以预测其耐久性并评估其在艺术品中的行为。通过加速老化实验,并与艺术品中观察到的自然老化进行比较,该研究揭示了发色团的形成和增塑剂的释放是关键过程;特别是,逐渐变暗被认为是退化过程的早期指标,在FTIR或NMR光谱检测到结构变化之前。增塑剂损失引起玻璃化转变温度的增加,从7°C到高于室温的温度,影响粘合剂的内聚强度,并有助于艺术品中材料的分离。研究结果强调了预防性保护措施的重要性,以减轻基于PVAC的艺术品中的退化问题。
    While extensive research has focused on understanding the degradation mechanisms of Poly(vinyl acetate) (PVAC) paint under different environmental conditions, limited attention has been paid to the long-term stability of PVAC-based white glues, especially when used in artworks. This study investigates the accelerated degradation, under simulated photoaging, and isothermal treatment of a commercial PVAC-based white glue considered representative of this class of materials used in contemporary artworks to predict its durability and assess its behavior in art objects. Through accelerated aging experiments and comparison with natural aging observed in artworks, the study reveals the formation of chromophores and the release of plasticizers as key processes; in particular, the progressive darkening was considered an early indicator of degradation processes, before structural changes could be detected by FTIR or NMR spectroscopies. The plasticizer loss induces an increase in glass transition temperature, from 7 °C to temperatures higher than room temperature, affecting the adhesive\'s cohesive strength and contributing to the detachment of materials in artworks. The findings underscore the importance of preventive conservation measures to mitigate degradation issues in PVAC-based artworks.
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  • 文章类型: Journal Article
    尽管基于可见光的立体光刻(SLA)代表了一种经济实惠的技术,用于3D支架的快速成型,用于体外支持细胞,它的潜力可能受到缺乏功能性光固化生物材料的限制,这些材料可以在微米分辨率下进行SLA结构。即使创新的光复合材料显示出仿生,生物活性,或通过将无机颗粒加载到光敏聚合物基质中来设计生物传感特性,主要示例依赖于基于UV辅助挤出的低分辨率工艺。这里,通过将聚乙二醇二丙烯酸酯(PEGDA)水凝胶与多分支金纳米颗粒(NP)混合,获得了SLA可印刷的复合材料。通过实施涉及共价接枝具有C=C侧基部分的烯丙胺分子的官能化方案,将NP工程化以与PEGDA基质共聚。调整金纳米复合材料的配方,以通过基于可见光的SLA实现复合支架的高分辨率快速成型。此外,事实证明,与聚合物混合后和激光成型后,金NP仍然保留其独特的等离子体性质,可以通过表面增强拉曼光谱(SERS)用于分析物的光学检测。作为概念的证明,使用拉曼探针分子成功证明了3D打印等离子体支架的SERS传感性能(例如,4-巯基苯甲酸)从未来扩展到实时感知培养物中释放的细胞特异性标志物的角度来看。最后,生物相容性试验初步证明,嵌入的NPs也通过诱导生理性细胞骨架重排发挥了关键作用,进一步证实了这种混合纳米复合材料作为基于激光的生物打印的突破性材料的潜力。
    Although visible light-based stereolithography (SLA) represents an affordable technology for the rapid prototyping of 3D scaffolds for in vitro support of cells, its potential could be limited by the lack of functional photocurable biomaterials that can be SLA-structured at micrometric resolution. Even if innovative photocomposites showing biomimetic, bioactive, or biosensing properties have been engineered by loading inorganic particles into photopolymer matrices, main examples rely on UV-assisted extrusion-based low-resolution processes. Here, SLA-printable composites were obtained by mixing a polyethylene glycol diacrylate (PEGDA) hydrogel with multibranched gold nanoparticles (NPs). NPs were engineered to copolymerize with the PEGDA matrix by implementing a functionalization protocol involving covalent grafting of allylamine molecules that have C═C pendant moieties. The formulations of gold nanocomposites were tailored to achieve high-resolution fast prototyping of composite scaffolds via visible light-based SLA. Furthermore, it was demonstrated that, after mixing with a polymer and after laser structuring, gold NPs still retained their unique plasmonic properties and could be exploited for optical detection of analytes through surface-enhanced Raman spectroscopy (SERS). As a proof of concept, SERS-sensing performances of 3D printed plasmonic scaffolds were successfully demonstrated with a Raman probe molecule (e.g., 4-mercaptobenzoic acid) from the perspective of future extensions to real-time sensing of cell-specific markers released within cultures. Finally, biocompatibility tests preliminarily demonstrated that embedded NPs also played a key role by inducing physiological cell-cytoskeleton rearrangements, further confirming the potentialities of such hybrid nanocomposites as groundbreaking materials in laser-based bioprinting.
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  • 文章类型: Journal Article
    长链非编码RNA(lncRNA)作为转录调节因子在疾病中具有重要作用,mRNA加工调节剂和蛋白质合成因子。然而,传统的检测lncRNA的方法耗时耗力,lncRNA的功能仍在探索中。这里,我们提出了一种基于表面增强拉曼光谱(SERS)的生物传感器,用于检测与肝癌(LC)相关的lncRNA以及原位细胞成像。使用双SERS探头,lncRNA(DAPK1-215)的定量检测可以通过靶触发的核心卫星纳米结构的组装以952aM的超低检测限实现。并且该测定的可靠性可以通过能够进行信号动态校准的内标探针以0.9923的R2值进一步提高。同时,使用SERS成像方法,与正常细胞相比,在LC细胞中观察到DAPK1-215主要分布在细胞质中的高表达。此外,细胞功能检测结果显示,DAPK1-215通过显著降低死亡相关蛋白激酶结构域的表达,促进LC的迁移和侵袭。这种基于SERS的生物传感器的开发可以为探索lncRNA的表达提供灵敏而特异的方法,lncRNA将是筛选LC的潜在生物标志物。
    Long-stranded non-coding RNAs (lncRNA) have important roles in disease as transcriptional regulators, mRNA processing regulators and protein synthesis factors. However, traditional methods for detecting lncRNA are time-consuming and labor-intensive, and the functions of lncRNA are still being explored. Here, we present a surface enhanced Raman spectroscopy (SERS) based biosensor for the detection of lncRNA associated with liver cancer (LC) as well as in situ cellular imaging. Using the dual SERS probes, quantitative detection of lncRNA (DAPK1-215) can be achieved with an ultra-low detection limit of 952 aM by the target-triggered assembly of core-satellite nanostructures. And the reliability of this assay can be further improved with the R2 value of 0.9923 by an internal standard probe that enables the signal dynamic calibration. Meanwhile, the high expression of DAPK1-215 mainly distributed in the cytoplasm was observed in LC cells compared with the normal ones using the SERS imaging method. Moreover, results of cellular function assays showed that DAPK1-215 promoted the migration and invasion of LC by significantly reducing the expression of the structural domain of death associated protein kinase. The development of this biosensor based on SERS can provide a sensitive and specific method for exploring the expression of lncRNA that would be a potential biomarker for the screening of LC.
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  • 文章类型: Journal Article
    表面增强拉曼光谱(SERS)利用分子振动的指纹特征来识别和检测物质。然而,在传统的单焦点激励场景中,其目的的信号采集效率受到限制。此外,样品在SERS基底上的不均匀分布会导致信号稳定性差,同时限制激励功率以避免样品损坏。SERS检测系统总是需要精确调整焦距和光斑尺寸,这使得即时测试应用变得困难。这里,我们提出了一种采用真空自组装热压方法嵌入钛酸钡微球阵列(BTMA)的SERS微流控芯片,用于SERS检测,同时提高了灵敏度和稳定性。由于光子纳米射流和定向天线效应,高折射率微球是完美的微透镜,用于有效的光聚焦和信号收集。BTMA不仅可以将激发光束分散到均匀覆盖目标的焦点阵列中,并且信号波动非常低,但放大功率阈值以获得更高的信号强度。我们在芯片上进行了原理验证实验,以使用免疫磁性标签和免疫SERS标签检测细菌。连同磁性和超声波操作,流中的目标细菌均匀地聚集在BTMA的焦平面上。它显示了5个细胞/mL的检测限,优异的信号再现性(误差4.84%),在X-Y平面上具有500μm的出色位置公差(误差〜5.375%)。可见BTMA-SERS微流控芯片能有效解决SERS检测中灵敏度与稳定性的矛盾。
    Surface enhanced Raman spectroscopy (SERS) utilizes the fingerprint features of molecular vibrations to identify and detect substances. However, in traditional single focus excitation scenarios, its signal collection efficiency of the objective is restricted. Furthermore, the uneven distribution of samples on the SERS substrate would result in poor signal stability, while the excitation power is limited to avoid sample damage. SERS detection system always requires precise adjustment of focal length and spot size, making it difficult for point-of-care testing applications. Here, we proposed a SERS microfluidic chip with barium titanate microspheres array (BTMA) embedded using vacuum self-assembled hot-pressing method for SERS detection with simultaneous enhancement of sensitivity and stability. Due to photonic nano-jets and directional antenna effects, high index microspheres are perfect micro-lens for effective light focusing and signal collecting. The BTMA can not only disperse excitation beam into an array of focal points covering the target uniformly with very low signal fluctuation, but enlarge the power threshold for higher signal intensity. We conducted a proof-of-principle experiment on chip for the detection of bacteria with immuno-magnetic tags and immuno-SERS tags. Together with magnetic and ultrasonic operations, the target bacteria in the flow were evenly congregated on the focal plane of BTMA. It demonstrated a limit of detection of 5 cells/mL, excellent signal reproducibility (error∼4.84%), and excellent position tolerance of 500 μm in X-Y plane (error∼5.375%). It can be seen that BTMA-SERS microfluidic chip can effectively solve the contradiction between sensitivity and stability in SERS detection.
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  • 文章类型: Journal Article
    DNA折纸是一个灵活的平台,用于精确组织纳米物体,实现从生物医学到纳米光子学的众多应用。其巨大的潜力源于其高度的灵活性,允许定制的结构,以满足特定的要求。通过折叠从共同的基底产生不同的最终结构的能力显著增强了设计多样性,并且经常发生在液体中。这项研究描述了一种新颖的方法,该方法将自上而下的光刻技术与自下而上的DNA折纸技术相结合,以控制DNA折纸的折叠以及在预图案化表面上的吸附。使用这种方法,在硅表面上制造可调谐等离子体二聚体纳米阵列。这涉及使用电子束光刻在表面上创建吸附位点,并利用用两个金纳米颗粒(AuNP)功能化的DNA折纸的自组织吸附。DNA折纸螺旋的期望折叠可以通过吸附位点的大小和形状来控制。该方法可以例如用于调整折纸模板上的AuNP二聚体的中心到中心距离。为了证明这种技术的效率,染料分子的拉曼信号(羧基四甲基罗丹明,研究了涂在AuNP表面上的TAMRA)。这些发现突出了可调DNA折纸基等离子体纳米结构在许多应用中的潜力。
    DNA origami is a flexible platform for the precise organization of nano-objects, enabling numerous applications from biomedicine to nano-photonics. Its huge potential stems from its high flexibility that allows customized structures to meet specific requirements. The ability to generate diverse final structures from a common base by folding significantly enhances design variety and is regularly occurring in liquid. This study describes a novel approach that combines top-down lithography with bottom-up DNA origami techniques to control folding of the DNA origami with the adsorption on pre-patterned surfaces. Using this approach, tunable plasmonic dimer nano-arrays are fabricated on a silicon surface. This involves employing electron beam lithography to create adsorption sites on the surface and utilizing self-organized adsorption of DNA origami functionalized with two gold nanoparticles (AuNPs). The desired folding of the DNA origami helices can be controlled by the size and shape of the adsorption sites. This approach can for example be used to tune the center-to-center distance of the AuNPs dimers on the origami template. To demonstrate this technique\'s efficiency, the Raman signal of dye molecules (carboxy tetramethylrhodamine, TAMRA) coated on the AuNPs surface are investigated. These findings highlight the potential of tunable DNA origami-based plasmonic nanostructures for many applications.
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