金纳米棒负载的静电纺丝纤维的制备及其表面增强拉曼光谱性能

为简单有效地制备高活性表面增强拉曼光谱(Surface-enhanced Raman Spectroscopy,SERS)基底。本文采用静电纺丝聚乙烯醇(PVA)/聚丙烯酸(PAA)纳米纤维为支撑材料,通过直接浸泡的方法,利用金纳米棒与电纺纤维之间的静电力,使纳米棒在纤维表面自组装,得到了性能优异的SERS基底。通过透射电子显微镜、扫描电子显微镜对金纳米棒以及不同状态下的电纺纤维的形貌进行表征,结果表明,金纳米棒均匀且密集地负载在纤维表面。通过设置不同的浸泡时间确定了金纳米棒组装平衡的时间为12 h,并通过调控纺丝时间和金纳米棒的浓度发现随着纺丝时间和金纳米棒浓度的增加,复合纤维膜SERS增强效果随之提升。该复合纤维膜具有优异的SERS均匀性,并且能够检测到浓度低至10~(-10)mol/L的4-氨基苯硫酚的存在。     

Oxadiazole‐2‐thiol Adsorption on Gold Nanorods: A Joint Theoretical and Experimental Study by Using SERS,XPS, and DFT

The chemisorption of 1,3,4‐oxadiazole‐2‐thiol (ODT) on gold nanorods has been investigated by using surface‐enhanced Raman spectroscopy (SERS) and density functional theory (DFT). Although most of the SERS spectra have remarkable similarity to the normal Raman spectra of the pure analyte, the adsorption of ODT on a gold surface leads to a drastic change in its Raman spectrum and distinct vibrational features are obtained with gold nanorods and spherical nanoparticles. Simulated Raman spectra for hybrid systems that consist of an oxadiazole moiety coordinated to a Au₂₀ gold cluster provided valuable information about the coordination mode and enabled us to assign vibration modes.     

Raman reporter-coated gold nanorods and their applications in multimodal optical imaging of cancer cells

We report the preparation of a kind of surface-enhanced Raman scattering (SERS) tags and explore their applications in multifunctional optical imaging of cancer cells. The proposed nanoparticles (SERS tags) are prepared by connecting dye molecules directly onto the surfaces of gold nanorods through Au–S or Au–N interactions. The dye molecules are used as Raman reporters, while gold nanorods are used as enhanced materials due to their localized surface plasmon resonance effect. Multilayered polymers are further coated onto the surfaces of the nanoparticles to reach better stability and biocompatibility. Gold nanorods with different aspect ratios and different dye molecules conjugated are compared in order to achieve the diversity of SERS tags and find out the optimized condition of SERS tags with the highest signal intensity. Our experiments show that the resulting nanoparticles, which are uptaken by cancer cells, can provide not only dark field cells images but also multiplexing SERS images.     

SERS标记的金纳米棒探针用于免疫检测

报道了基于金纳米棒表面增强拉曼散射(SERS)的免疫检测. 将拉曼活性分子对巯基苯甲酸吸附于金纳米棒表面, 制备出SERS标记的金纳米棒探针. 该探针和蛋白抗体结合形成SERS标记抗体. 通过SERS标记抗体、待测抗原和俘获抗体(固体基底上修饰的抗体, 即俘获抗体)之间的免疫应答反应, 将金纳米棒探针组装到固体基底上, 形成SERS标记抗体-抗原-俘获抗体 “三明治”夹心复合体. 待测抗原浓度越大, 固体基底上俘获的金纳米棒探针的数目越多, 从而可通过SERS信号的强弱来检测待测抗原的浓度. 由于金纳米棒的表面等离子体共振(SPR)峰位置可以在较宽的范围内调控, 可通过激发光和SPR的耦合来提高SERS信号, 从而提高免疫检测的灵敏度. 单组分抗原可检出的浓度范围高于1×10－8 mg/mL.     

Immobilization of gold nanorods onto acid-terminated self-assembled monolayers via electrostatic interactions

We report the immobilization of gold nanorods onto self-assembled monolayers (SAMs) of 16-mercaptohexadecanoic acid (16-MHA). The simple two step protocol involves formation of a SAM of 16-MHA molecules onto gold-coated glass slides and subsequent immersion of these slides into the gold nanorod solution. The nanorods, formed by a seed-mediated, surfactant-assisted synthesis protocol, are stabilized in solution due to surface modification by the surfactant cetyltrimethylammonium bromide (CTAB). Attractive electrostatic interactions between the carboxylic acid group on the SAM and the positively charged CTAB molecules are likely responsible for the nanorod immobilization. UV-vis spectroscopy has been used to follow the kinetics of the nanorod immobilization. The nature of interaction between the gold nanorods and the 16-MHA SAM has been probed by Fourier transform infrared spectroscopy (FTIR). The surface morphology of the immobilized rods is studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM) measurements. SEM was also used to determine the density of the immobilized nanorods as a function of the pH of immobilization. Control over the surface coverage of the immobilized gold nanorods has been demonstrated by simple pH variation. Such well-dispersed immobilized gold nanorods with control over the surface coverage could be interesting substrates for applications such as surface-enhanced Raman spectroscopy (SERS).     

以Au/Cu纳米棒为基底的肺腺癌组织的特征表面增强拉曼光谱研究

通过金铜共混法制备了Au/Cu合金纳米棒,研究了铜掺杂对金纳米棒等离子体共振吸收和结构的影响,探究了Au/Cu合金纳米棒的等离子体共振拉曼增强效应.以Au/Cu合金纳米棒为基底对肺腺癌组织和癌旁正常组织进行了表面增强拉曼光谱检测.结果显示,癌变组织具有比癌旁正常组织更强的拉曼信号峰,位于1250,1344,1408,1568,1608和2560 cm~(-1)附近的拉曼峰分别与蛋白质的AmideⅡ氨基化合物、C—H弯曲振动、核酸中CH_3的对称变角振动、蛋白质色氨酸惰性环振动、蛋白质酰胺I谱带分子间反平行β-折叠的C—O健伸缩振动和蛋白质的巯基(S—H)伸缩振动有关,2936 cm~(-1)附近的拉曼峰为蛋白质CH_2的对称伸缩振动和CH_3的反对称伸缩振动共同作用产生.以铜掺杂的金纳米棒为基底的表面增强拉曼光谱法有望成为检测肺癌组织的有效手段.     

A rapid method for detection of genetically modified organisms based on magnetic separation and surface-enhanced Raman scattering

In this study, a new method combining magnetic separation (MS) and surface-enhanced Raman scattering (SERS) was developed to detect genetically modified organisms (GMOs). An oligonucleotide probe which is specific for 35 S DNA target was immobilized onto gold coated magnetic nanospheres to form oligonucleotide-coated nanoparticles. A self assembled monolayer was formed on gold nanorods using 5,5'-dithiobis (2-nitrobenzoic acid) (DTNB) and the second probe of the 35 S DNA target was immobilized on the activated nanorod surfaces. Probes on the nanoparticles were hybridized with the target oligonucleotide. Optimization parameters for hybridization were investigated by high performance liquid chromatography. Optimum hybridization parameters were determined as: 4 μM probe concentration, 20 min immobilization time, 30 min hybridization time, 55 °C hybridization temperature, 750 mM buffer salt concentration and pH: 7.4. Quantification of the target concentration was performed via SERS spectra of DTNB on the nanorods. The correlation between the target concentration and the SERS signal was found to be linear within the range of 25-100 nM. The analyses were performed with only one hybridization step in 40 min. Real sample analysis was conducted using Bt-176 maize sample. The results showed that the developed MS-SERS assay is capable of detecting GMOs in a rapid and selective manner.     

Effect of layer structures of gold nanoparticle films on surface enhanced Raman scattering

Using a method of collecting nanoparticles at a water/hexane interface in a close-packed monolayer film and transferring such films onto a solid substrate, three-dimensional multilayer films of nanoparticles were formed. The packed nanoparticles were gold nanospheres (NS) with a 26 nm diameter or gold nanorods (NR) with a 31 nm diameter and 74 nm length. We investigated variations in the surface enhanced Raman scattering (SERS) intensities from such nanoparticle films as the layer compositions were changed. The films stacked with NR layers generated much higher SERS intensity than those of NS layers. The SERS intensities from both kinds of films increased as the number of layers were increased. However, when the NR layer and NS layer were stacked alternately, SERS intensity varied in a zigzag fashion. It was found that the structure of top layer plays a distinguishable role in generating strong SERS enhancement while the lower layers contribute to SERS with less dependency on structures. Interlayer coupling as well as intralayer coupling was considered in order to explain the observations.     

银纳米微球和银纳米棒自组装膜的制备及SERS研究

采用硼氢化钠还原硝酸银,用振荡器在不同转速下振荡得到单分散的银纳米微球和银纳米棒,再将银纳米微球及银纳米棒自组装于被3-氨丙基-三甲氧基硅烷(APTMS)修饰的玻璃基片上,制得了具有表面增强拉曼(SERS)活性的基底,分别以罗丹明6G(R6G)和罗丹明B(RB)为探针分子对这两种基底进行SERS活性检测,结果发现这两种基底均为较理想的SERS衬底。     

Aspect ratio dependence on surface enhanced Raman scattering using silver and gold nanorod substrates

Silver and gold nanorods with aspect ratios from 1 to 16 have been used as substrates for surface enhanced Raman spectroscopy (SERS) in colloidal solution. The nanorod aspect ratio is varied to give different degrees of overlap between the nanorod longitudinal plasmon band and excitation source in order to determine its effect on overall surface enhancement. Results suggest that enhancement factors are a factor of 10-10(2) greater for substrates that have plasmon band overlap with the excitation source than for substrates whose plasmon bands do not.     

Starfruit-shaped gold nanorods and nanowires: synthesis and SERS characterization

Recently, branched and star-shaped gold nanoparticles have received significant attention for their unique optical and electronic properties, but most examples of such nanoparticles have a zero-dimensional shape with varying numbers of branches coming from a quasi-spherical core. This report details the first examples of higher-order penta-branched gold particles including rod-, wire-, and platelike particles which contain a uniquely periodic starfruitlike morphology. These nanoparticles are synthesized in the presence of silver ions by a seed-mediated approach based on utilizing highly purified pentahedrally twinned gold nanorods and nanowires as seed particles. The extent of the growth can be varied, leading to shifts in the plasmon resonances of the particles. In addition, the application of the starfruit rods for surface-enhanced Raman spectroscopy (SERS) is demonstrated.     

Facile fabrication of large area of aggregated gold nanorods film for efficient surface-enhanced Raman scattering

An effective and facile method for fabrication of large area of aggregated gold nanorods (AuNRs) film was proposed by self-assembly of AuNRs at a toluene/water interface for the first time. It was found that large area of aggregated AuNRs film could be formed at the interface of toluene and water due to the interfacial tension between the two phases. The obtained large area of aggregated AuNRs film exhibits strong surface-enhanced Raman scattering (SERS) activity with 4-aminothiophenol (4-ATP) and 2-aminothiophenol (2-ATP) as the probe molecules based on the strong electromagnetic coupling effect between the very adjacent AuNRs. Enhancement factors (EF) were used to estimate the SERS activity of the aggregated AuNRs film, which is obtained to be 1.7x10(5) for 7a vibration of 4-ATP. SERS intensity is compared with AuNRs deposited directly on glass, indicating high SERS activity and reproducibility of the aggregated AuNRs film. In addition, SERS activity has also been successfully demonstrated for dye molecule (Rhodamin 6G (R6G)) and biological small molecule (adenine) on the aggregated AuNRs film, showing great potential of the aggregated AuNRs film as a convenient and powerful SERS substrate for biological tags and biological molecular detection.     

Au nanorod arrays tailored for surface-enhanced Raman spectroscopy.

We have demonstrated surface-enhanced Raman spectroscopy (SERS) on arrays of Au nanorods aligned in line by a dynamic oblique deposition technique. For light polarized along the major axes of the nanorods, the plasma resonance of the Au nanorods has been tuned to a wavelength suitable for Raman spectroscopy. Raman scattering on the discrete nanorods is significantly enhanced compared with that on semicontinuous Au films. Since the preparation process is physically bottom-up, it is robust in its selection of the materials and is useful for providing SERS sensors at low cost.     

“Two‐Step” Raman Imaging Technique To Guide Chemo‐Photothermal Cancer Therapy

Graphene oxide‐wrapped gold nanorods (GO@AuNRs) offer efficient drug delivery as well as NIR laser photothermal therapy (PTT) in vitro and in vivo. However, no real‐time observation of drug release has been reported to better understand the synergy of chemotherapy and PTT. Herein, surface‐enhance Raman spectroscopy (SERS) is employed to guide chemo‐photothermal cancer therapy by a two‐step mechanism. In the presence of GO as an internal standard, SERS signals of DOX (doxorubicin) loaded onto GO@AuNRs are found to be pH‐responsive. Both DOX and GO show strong SERS signals before the DOX@GO@AuNRs are endocytic. However, when the DOX@GO@AuNRs enter acidic microenvironments such as endosomes and/or lysosomes, the DOX signals start decreasing while the GO signals remain the same. This plasmonic antenna could be used to identify the appropriate time to apply the PTT laser during chemo‐photothermal therapy.     

Structural transition in the surfactant layer that surrounds gold nanorods as observed by analytical surface-enhanced Raman spectroscopy

Surface-enhanced Raman spectroscopy (SERS) of gold nanorods in cetyltrimethylammonium bromide solution has been used to analyze the interfacial surfactant structure based on the distance-dependent electromagnetic enhancement. The spectra were consistent with a surfactant bilayer oriented normal to the surface. As the surfactant concentration was reduced, a structural transition in the surfactant layer was observed through a sudden increase in the signal from the alkane chains. The structural transition was shown to influence the displacement of the surfactant layer by thiolated poly(ethylene glycol). The monodisperse and thoroughly characterized gold nanorod samples yield consistent enhancement factors that were compared to electromagnetic simulations.     

Polarized surface enhanced Raman and absorbance spectra of aligned silver nanorod arrays

Polarized surface-enhanced Raman scattering (SERS) and UV-vis absorbance spectra were measured for a nonplanar Ag nanorod array substrate prepared by oblique angle vapor deposition. The anisotropy of the SERS polarization was shown to differ from that of the polarized UV-vis absorbance. The maximum SERS intensity was observed in the polarization direction perpendicular to the long axis of the Ag nanorods, while the UV-vis absorbance was strongly polarized along the direction of the long axis of the nanorod array. Analysis of the polarization data showed that molecular orientation was not the cause of the anisotropic SERS scattering. Rather, the SERS anisotropy was primarily attributed to the lateral arrangement of the three-dimensional tilted nanorod lattice in which highly localized plasmon modes are created by strong electromagnetic coupling between adjacent metallic nanorods.     

Synthesis, characterization and SERS activity of Au-Ag nanorods

The formation mechanism and morphology of Au-Ag bimetallic colloidal nanoparticles depend on the composition. Ag coated Au colloidal nanoparticles have been prepared by deposition of Ag through chemical reduction on performed Au colloid. The composition of the Au(100-x)-Ag(x) particles was varied from x=0 to 50. The obtained colloids were characterized by UV-vis spectroscopy and transmission electron microscopy (TEM). The Au(80)-Ag(20) colloid consists of alloy nanorods with dimension of 25nmx100nm. The activity of these nanorods in surface enhanced Raman spectroscopy (SERS) was checked by using sodium salicylate as an adsorbate probe. Intense SERS bands are observed indicating its usefulness as a SERS substrate in near infrared (NIR) laser excitation.     

Quantitation of metal content in the silver-assisted growth of gold nanorods

The seed-mediated approach to making gold nanorods in aqueous surfactant solutions has become tremendously popular in recent years. Unlike the use of strong chemical reductants to make spherical gold nanoparticles, the growth of gold nanorods requires weak reducing conditions, leading to an unknown degree of gold reduction. The metal content of gold nanorods, made in high yield in the presence of silver ion, is determined by inductively coupled plasma atomic emission spectroscopy. Through the use of the known gold concentration in nanorods, molar extinction coefficients are calculated for nanorods of varying aspect ratios from 2.0 to 4.5. The extinction coefficients at the longitudinal plasmon band peak maxima for these nanorods vary from 2.5x10(9) to 5.5x10(9) M-1 cm-1, respectively, on a per-particle basis. Many of the gold ions present in the growth solution remain unreacted; insights into the growth mechanism of gold nanorods are discussed.     

Surface-enhanced Raman scattering: realization of localized surface plasmon resonance using unique substrates and methods

Surface-enhanced Raman scattering (SERS) enhancement and the reproducibility of the SERS signal strongly reflect the quality and nature of the SERS substrates because of diverse localized surface plasmon resonance (LSPR) excitations excited at interstitials or sharp edges. LSPR excitations are the most important ingredients for achieving huge enhancements in the SERS process. In this report, we introduce several gold and silver nanoparticle-based SERS-active substrates developed solely by us and use these substrates to investigate the influence of LSPR excitations on SERS. SERS-active gold substrates were fabricated by immobilizing colloidal gold nanoparticles on glass slides without using any surfactants or electrolytes, whereas most of the SERS-active substrates that use colloidal gold/silver nanoparticles are not free of surfactant. Isolated aggregates, chain-like elongated aggregates and two-dimensional (2D) nanostructures were found to consist mostly of monolayers rather than agglomerations. With reference to correlated LSPR and SERS, combined experiments were carried out on a single platform at the same spatial position. The isolated aggregates mostly show a broadened and shifted SPR peak, whereas a weak blue-shifted peak is observed near 430 nm in addition to broadened peaks centered at 635 and 720 nm in the red spectral region in the chain-like elongated aggregates. In the case of 2D nanostructures, several SPR peaks are observed in diverse frequency regions. The characteristics of LSPR and SERS for the same gold nanoaggregates lead to a good correlation between SPR and SERS images. The elongated gold nanostructures show a higher enhancement of the Raman signal than the the isolated and 2D samples. In the case of SERS-active silver substrates for protein detection, a new approach has been adopted, in contrast to the conventional fabrication method. Colloidal silver nanoparticles are immobilized on the protein functionalized glass slides, and further SERS measurements are carried out based on LSPR excitations. A new strategy for the detection of biomolecules, particularly glutathione, under aqueous conditions is proposed. Finally, supramolecular J-aggregates of ionic dyes incorporated with silver colloidal aggregates are characterized by SERS measurements and correlated to finite-difference time-domain analysis with reference to LSPR excitations. Figure SPR and SERS images for isolated, elongated and two-dimensional gold nanostructures     

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.