帽状铜纳米粒子的制备及表面增强拉曼散射活性研究

采用真空热蒸发法在SiO₂纳米粒子自组装单层膜上沉积铜薄膜制备了帽状铜纳米粒子。用扫描电镜、原子力显微镜和紫外-可见-近红外分光光度计对帽状复合纳米粒子的表面形貌和光学性质进行了表征。以亚甲基蓝和吡啶-(2-偶氮-4)间苯二酚为探针分子,研究了该复合纳米粒子的表面增强拉曼散射(SERS)活性。通过比较吸附在不同基底上的吡啶-(2-偶氮-4)间苯二酚的谱峰强度,探讨了SERS效应与表面等离子体共振(SPR)的关系。     

基于分子印迹与表面增强拉曼散射的蛋白质疾病标志物检测研究进展

异常的蛋白质表达与疾病的发生与发展密切相关,因此蛋白质已作为疾病标志物广泛应用于疾病的早期诊断、治疗监测和预后评估.然而,临床样本中的蛋白质疾病标志物通常含量极低,并存在高丰度的基质干扰,对检测方法的特异性和灵敏度提出挑战.目前,蛋白质疾病标志物的检测方法主要是免疫分析.但是,免疫分析主要依赖抗体进行特异性识别,而抗体...     

Determination of Saxitoxin by Aptamer-Based Surface-Enhanced Raman Scattering

Saxitoxin is one of the most harmful paralytic shellfish toxins due to its high toxicity and adverse effects on the environment and human health. Aptasensors provide simple detection procedures because they have the advantages of chemical stability, easy synthesis and modification, and high convenience in signal transformation. Surface-enhanced Raman scattering (SERS) is an analytical technique that amplifies the analytical signals of molecules at extremely low concentrations, or even at the single molecule level, when the analyte is very close to rough metal surfaces or nanostructures. In this study, an SERS aptasensor is reported for the determination of saxitoxin for the first time. The optimized saxitoxin aptamer (M-30f) was modified on gold nanoparticles and served as the recognition element. Crystal violet was used as the Raman reporter without chemical bounding. The analytical principles of the aptasensor are that saxitoxin destabilized the conformations of the aptamer at high temperature conditions and altered the binding of crystal violet on the gold nanoparticles. In the presence of saxitoxin, the conformation of aptamer containing the G-quadruplex that selectively bound crystal violet unfolded to a large extent and hence the crystal violet molecules were released from gold nanoparticles with a reduced SERS signal. The effects of the gold nanoparticle size, the amount of DNA, aptamer density, sodium chloride concentration, and operation temperature upon the SERS determination were optimized. The resulting simple SERS aptasensor was developed with a satisfactory limit of detection (11.7?nM) and selectivity. The application for the analysis of real shellfish samples with simple procedures demonstrates that this SERS aptasensor is promising for on-site applications.     

虚拟分子印迹与表面增强拉曼散射联用技术用于孔雀石绿的超灵敏检测

采用抗坏血酸还原法制备Ag球粒子,然后用3-（甲基丙烯酰氧）丙基三甲氧基硅烷使其表面硅烷化,最后用虚拟模板分子松香酸代替模板分子孔雀石绿与功能单体甲基丙烯酰胺反应合成虚拟印迹聚合物.结果表明,生成的"核-壳"式复合基底比Ag的表面增强拉曼散射（SERS）增强效果显著,其对孔雀石绿的最低检测浓度达到10^-11 mol/L.该方法实现了背景噪音的消除,提高了分析结果的准确性,为有机染料的超灵敏检测提供了参考.     

Silver Nanowire-Templated Molecular Nanopatterning and Nanoparticle Assembly for Surface-Enhanced Raman Scattering

Developing simple and cost-efficient methods for fabricating molecular patterns is of great importance in the field of nanoscience and nanotechnology. Here, a simple and convenient method was developed for fabricating nanopatterns composed of positively charged silane molecules by using silver nanowires as templates. The as-obtained silane pattern copies the shape of the silver nanowires and is only 0.7 nm thick, which can later be used for templated assembly of small molecules and nanoparticles of opposite charges. As a proof of concept, the resultant assembly could be further used for surface-enhanced Raman scattering.     

耐尔蓝A在银溶胶上的表面增强拉曼光谱特征

研究了在不同耐尔蓝Ａ浓度，银溶胶，激发波长和ｐＨ值以及碘离子存在下，耐尔蓝Ａ在银溶胶上的表面增强拉曼光谱特征。     

氧化石墨烯/金银纳米粒子复合材料的制备及其SERS效应研究

近年来,氧化石墨烯/金银纳米粒子复合材料由于其优异的表面增强拉曼散射（SERS）性能引起了人们极大的关注,在污染物检测、化学传感和癌症诊断等领域具有重要的应用价值。本文综述了氧化石墨烯片层上修饰金银纳米粒子、氧化石墨烯包覆金银纳米粒子、氧化石墨烯附着在金银纳米粒子层三种氧化石墨烯/金银纳米粒子复合材料的制备方法,对其SERS效应进行了详细介绍。SERS研究表明,结合了金银纳米粒子与氧化石墨烯两种材料各自在SERS研究与应用中的优势,氧化石墨烯/金银纳米粒子复合材料的SERS性能比单纯金银纳米粒子更加优异。氧化石墨烯在其中起到了化学增强、分子富集、钝化保护、荧光猝灭的重要作用。氧化石墨烯/金银纳米粒子复合材料在表面增强拉曼光谱中具有广阔的应用前景。     

Determination of Carcinoembryonic Antigen by Surface-Enhanced Raman Spectroscopy Using Gold Nanobowl Arrays

Surface-enhanced Raman scattering (SERS) based on the double-antibody sandwich format is reported for the determination of carcinoembryonic antigen. Ordered gold nanobowl arrays were fabricated and conjugated with anticarcinoembryonic as capturing substrates, and gold nanoshells, adsorbed with 4-mercaptobenzonic acid, were modified with anticarcinoembryonic antigen as labeling tags. After the carcinoembryonic antigen was captured on ordered gold nanobowl arrays, the labeling tags were bonded to the captured carcinoembryonic antigen. The interaction of SERS substrates (ordered gold nanobowl arrays) and SERS labels (gold nanoshells) showed high sensitivity and a low detection limit for carcinoembryonic antigen. The linear dynamic range of SERS for carcinoembryonic antigen was from 5?pg/mL to 100?ng/mL with a linear relationship between carcinoembryonic antigen concentration and SERS intensity. The detection limit was 1.73?pg/mL. SERS detection may be used for other cancer biomarkers and provides potential for the clinical diagnosis of cancer biomarkers.     

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.     

黄曲霉素B2分子吸附在银团簇的表面增强拉曼散射机理

采用密度泛函理论（DFT）B3LYP方法,6-311G（d,p）（C,H,O）/LANL2DZ（Ag）基组,计算了黄曲霉素B₂（AFB₂）分子吸附在Ag₂团簇的表面增强拉曼散射（SERS）光谱和预共振拉曼光谱,并与实验结果比较. 结果显示：AFB₂分子在基态Ag₂团簇表面吸附时,增强因子最大达到10²,对应吡喃（pyrane）环C=O伸缩振动,主要是由AFB₂分子周围化学环境改变而引起的基态静极化率改变导致的化学增强. 不同激发波长下的AFB₂分子预共振拉曼光谱的增强强度不同：电荷转移态激发波长为1144 和544 nm时拉曼信号增强了10²倍,而选择电荷转移预共振波长432和410 nm作为入射光时,其拉曼信号增强了10⁴倍,增强机理为银团簇和黄曲霉素分子之间的电荷转移共振增强. 因此通过改变入射光波长,选择电荷转移共振激发波长,更有利于强致癌物AFB₂分子的痕量检测.     

pH值和阴离子对吡啶2,6-二羧酸在金纳米颗粒表面的增强拉曼散射的影响

表面增强拉曼散射(SERS)被用于检测细菌芽抱中的一种重要的标志物吡啶2,6-羧酸(DPA).以聚乙烯吡啶烷酮(PVP)为粘合剂,将60 nm的金粒子组装到表面打磨光滑的金电极上,制备稳定、灵敏的SERS基底.通过不同pH值下吸附在金基底上的DPA的SERS特征,考察DPA分子吸附构型发生的变化,并分析酸根离子对其吸附...     

表面增强拉曼光谱内标法测定亚胺硫磷农残含量

采用柠檬酸钠还原法制备了具有表面增强拉曼散射(SERS)活性的纳米银溶胶,进而利用亚胺硫磷(Phosmet)吸附于纳米银胶表面使其产生SERS光谱,并对Phosmet的含量进行了测定。选择硫氰化钾(KSCN)为内标物,通过不同浓度亚胺硫磷的拉曼特征峰(S—P伸缩振动503 cm-1)与内标物SCN-的特征峰(2 120 cm-1)峰高的相对强度比,建立线性回归方程。结果表明:Phosmet的线性范围为5.0×10-7~1.2×10-5mol·L-1,相关系数为0.997 8;按7次空白实验所对应响应值IR的3倍标准偏差,计算得检出限为2.82×10-7mol·L-1;回收率为88.7%~110.2%,相对标准偏差(RSD)不大于8.0%。方法测定简单、操作方便、内标物干扰小,可应用于其他农残的分析测定。     

可循环SERS基底ZnO/Ag纳米材料合成和表征

利用简易、绿色、一锅煮的水热法合成了花状氧化锌/银复合纳米材料。然后利用各种光谱和显微技术对复合物进行了表征,并讨论了其表面增强拉曼(SERS)性能和光催化性能。结果表明氢氧化钠的量对于这种复合纳米材料的形貌和性能具有重要的调节作用。和其他形貌的氧化锌/银复合纳米材料相比较,花状氧化锌/银复合纳米材料具有最佳的光催化性能。同时进一步以花状氧化锌/银复合纳米材料作为SERS基底研究其表面增强拉曼性能,结果表明这种复合材料同时具有很好的表面增强拉曼性能。光催化和表面增强拉曼结果表明这种花状氧化锌/银复合纳米材料有望在有机物检测中作为一种具有很好的可循环性的新表面增强拉曼基底材料。     

可循环SERS基底ZnO/Ag纳米材料合成和表征

利用简易、绿色、一锅煮的水热法合成了花状氧化锌/银复合纳米材料。然后利用各种光谱和显微技术对复合物进行了表征,并讨论了其表面增强拉曼（SERS）性能和光催化性能。结果表明氢氧化钠的量对于这种复合纳米材料的形貌和性能具有重要的调节作用。和其他形貌的氧化锌/银复合纳米材料相比较,花状氧化锌/银复合纳米材料具有最佳的光催化性能。同时进一步以花状氧化锌/银复合纳米材料作为SERS基底研究其表面增强拉曼性能,结果表明这种复合材料同时具有很好的表面增强拉曼性能。光催化和表面增强拉曼结果表明这种花状氧化锌/银复合纳米材料有望在有机物检测中作为一种具有很好的可循环性的新表面增强拉曼基底材料。     

预聚集法制备单层银纳米粒子膜及其SERS活性研究

提出一种预聚集方法来制备单层银纳米粒子膜, 获得了高活性的表面增强拉曼散射基底. 利用紫外-可见吸收光谱、TEM, SEM等表征手段分析了预聚集程度对银纳米单层膜基底SERS活性的影响. 实验发现该方法制备的银纳米粒子膜的SERS活性与预聚集程度直接相关, 在最优参数下制备的SERS基底具有银颗粒分布均匀、SERS活性均一、增强效果好等优点. 实验分别以罗丹明6G (R6G)、3-巯基丙酸(3MPA)和9-氨基吖啶盐酸盐(9AA)为探针对所制备基底的SERS活性进行了测试, 结果均获得了高信噪比的SERS信号.     

Silver Molecularly Imprinting Polymer for the Determination of p-Nitroaniline by Surface Enhanced Raman Scattering

Molecular imprinting and surface enhanced Raman scattering (SERS) were used to prepare a core-shell Ag@molecularly imprinting polymer (MIP) for the determination of p-nitroaniline. The obtained Ag@MIP exhibits a detection limit of 10^?12 M, which demonstrates higher sensitivity toward p-nitroaniline than conventional approaches. In addition, the Ag@MIP shows good recyclability, and simultaneously offers better stability and high SERS activity for recognizing target molecules. To characterize the high SERS activity of the SERS-MIP hybrid material, a possible mechanism for the SERS substrate is proposed involving enhancement by the MIP. This study is expected to provide an alternative approach for the determination of p-nitroaniline in aqueous environments.     

基于Co3O4纳米粒子的“串联酶”活性检测葡萄糖的表面增强拉曼光谱策略

采用一种简单的湿化学法合成Co₃O₄纳米粒子(NPs),并将其作为一种"串联酶"(同时具有类过氧化物酶和类葡萄糖氧化酶活性)用于过氧化氢(H₂O₂)和葡萄糖的表面增强拉曼散射(SERS)光谱检测。作为一种灵敏的SERS底物,在pH=4.0的NaAc缓冲液条件下,Co₃O₄NPs可以催化葡萄糖和O₂生成葡萄糖酸和H₂O₂。然后H₂O₂可以氧化3,3′,5,5′-四甲基联苯胺(TMB),形成蓝色氧化产物氧化TMB(oxTMB),其在1188、1330、1610 cm^-1处表现出强烈的SERS信号。因此,我们开发了一种新的SERS策略来分析葡萄糖,检测限为1×10^-10mol·L^-1,表明Co₃O₄NPs具有生物传感器、免疫分析和医学研究的潜力。     

Characterization of the Interaction of 6-Thioguanine with Human Serum Albumin by Surface-Enhanced Raman Scattering and Molecular Modeling

The interaction of 6-thioguanine and human serum albumin was investigated by fluorescence, ultraviolet-visible absorption, and surface-enhanced Raman scattering. The fluorescence of human serum albumin decreased with the concentration of 6-thioguanine, and the fluorescence quenching of human serum albumin by 6-thioguanine was static. Molecular modeling showed that 6-thioguanine was located in the hydrophobic cavity in subdomain IIA of human serum albumin. Surface-enhanced Raman scattering was combined with density function theory to characterize the orientation of 6-thioguanine on gold and the 6-thioguanine functional groups bonded to human serum albumin. The 6-thioguanine was shown to be tilted on the gold surface by a N-C?S moiety. The binding sites of 6-thioguanine to human serum albumin were the NH and amino groups of the pyrimidine ring of 6-thioguanine. This study may provide information regarding the metabolism of anticancer pharmaceuticals in the human body and assist in the development of effective compounds.     

黄曲霉素B_2分子吸附在银团簇的表面增强拉曼散射机理

采用密度泛函理论(DFT)B3LYP方法,6-311G(d,p)(C,H,O)/LANL2DZ(Ag)基组,计算了黄曲霉素B2(AFB2)分子吸附在Ag2团簇的表面增强拉曼散射(SERS)光谱和预共振拉曼光谱,并与实验结果比较.结果显示:AFB2分子在基态Ag2团簇表面吸附时,增强因子最大达到102,对应吡喃(pyrane)环C=O伸缩振动,主要是由AFB2分子周围化学环境改变而引起的基态静极化率改变导致的化学增强.不同激发波长下的AFB2分子预共振拉曼光谱的增强强度不同:电荷转移态激发波长为1144和544 nm时拉曼信号增强了102倍,而选择电荷转移预共振波长432和410 nm作为入射光时,其拉曼信号增强了104倍,增强机理为银团簇和黄曲霉素分子之间的电荷转移共振增强.因此通过改变入射光波长,选择电荷转移共振激发波长,更有利于强致癌物AFB2分子的痕量检测.     

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.