Ag_核Au_壳金属复合纳米粒子的制备及表面增强拉曼光谱研究

在已制备好的Ag纳米粒子表面,通过化学还原的方法沉积生长Au包裹层,制备了粒子尺寸为50-70nm的Ag核Au壳复合纳米粒子.通过改变AuCl₄^-量,使Ag_100-xAu_x中Au的含量由x=0变为x=30.用UV-Vis吸收光谱和透射电子显微镜(TEM)对该结构纳米粒子进行了表征,并以对巯基苯胺(PATP)为探针分子进行表面增强拉曼光谱(SERS)研究.表面拉曼光谱表明,该结构的纳米粒子具有比Ag更强的SERS活性,随着Au:Ag比例的逐渐增加,其活性呈现先增大后减小的趋势,其最大增强约为Ag纳米粒子的10倍.     

Phytosynthesis of Au, Ag and Au-Ag bimetallic nanoparticles using aqueous extract and dried leaf of Anacardium occidentale

Present study reports a green chemistry approach for the biosynthesis of Au, Ag, Au-Ag alloy and Au core-Ag shell nanoparticles using the aqueous extract and dried powder of Anacardium occidentale leaf. The effects of quantity of extract/powder, temperature and pH on the formation of nanoparticles are studied. The nanoparticles are characterized using UV-vis and FTIR spectroscopies, XRD, HRTEM and SAED analyses. XRD studies show that the particles are crystalline in the cubic phase. The formation of Au core-Ag shell nanoparticles is evidenced by the dark core and light shell images in TEM and is supported by the appearance of two SPR bands in the UV-vis spectrum. FTIR spectra of the leaf powder before and after the bioreduction of nanoparticles are used to identify possible functional groups responsible for the reduction and capping of nanoparticles. Water soluble biomolecules like polyols and proteins are expected to bring about the bio-reduction.     

金银纳米粒子的复合组装及表面增强拉曼光谱研究

采用自组装技术在硅基底上进行金银纳米粒子的混合组装, 通过控制组装溶液中金银溶胶的体积比而控制基底上金银纳米粒子的密度. SEM结果显示金银呈亚单层均匀分布, 以吡啶为探针分子, 在不同波长的激发光下研究了纯金、银以及混合组装时的SERS效应. 利用金银在不同激发线下增强效应的不同以及探针分子吸附在金银纳米粒子表面主要谱峰相对强度差别的特点, 通过一系列校正以及差谱方法研究了金银共存时SERS效应的变化, 并分离出混合体系中金的增强行为, 结果表明在金银同时组装时吡啶的SERS谱峰特征主要表现为银纳米粒子的行为, 分离出的金SERS光谱特征接近银的行为, 说明金银纳米粒子之间产生了一定的耦合作用.     

Au/Ag核-壳结构纳米粒子的制备及其SERS效应

随着大量有关表面增强拉曼散射 (SERS)的实验和理论研究的开展 ,金属纳米粒子作为一类重要的 SERS增强介质 ,已引起了人们浓厚的研究兴趣 [1] .而 Au和 Ag作为最常用的活性基底物质 ,更是研究的热点 [2 ,3 ] .最近 ,美国印第安那大学的 Nie等 [4 ] 在单个银纳米粒子上 ,观察到高达 1 0 14 ～ 1 0 15的SERS因子 .同时 ,他们的另外一项工作表明银纳米粒子的形状和大小对 SERS活性有很大影响 [5] .但是 ,由于 Ag溶胶制备的重复性较差 ,且粒度分布不均匀 ,通过控制银颗粒大小而调控 SERS活性是相当困难的[6] .与 Ag相比 ,Au在可见光…     

Fabrication, Characterization, and Surface-Enhanced Raman Activity Study of Silver Coated Gold Nanoparticulate Films

This paper reports a study on the preparation of Ag-clad Au colloidal monolayer films by a combination of colloid self-assembly and liquid phase microwave high-pressure technique. Firstly, monodisperse Au nanoparticles prepared by microwave heating method were assembled onto a quartz slide. Then, these Au colloidal particles on the quartz surface acted as seeds for growing the Ag-clad Au composite particulate films. The obtained particulate films were characterized by UV-Vis spectra and atomic force microscopy. It was found that the thickness of the shell and thus the size of particles in the composite colloidal films could be controlled by deposition of Ag on the preformed Au colloidal particle film in the microwave reaction system, and such films significantly increased the surface-enhanced Raman scattering enhancement （SERS） ability compared with Au colloidal particle films. Their strong enhancement ability may mainly stem from relatively large particle consisting of Ag cladding as well as effective coupling among particles in the Ag-clad Au particle ftlms.     

Au-Ag合金纳米粒子制备及其表面增强拉曼光谱研究

首先采用柠檬酸钠法制得Au-Ag合金纳米种子, 然后采用盐酸羟胺生长法得到不同组成的Au-Ag合金纳米粒子. 在其UV-Vis光谱中只观察到一个位于单金属银和金之间的等离子体共振峰, 表明Au-Ag合金纳米粒子已经形成. TEM结果表明, 合金纳米粒子的粒径约为60 nm, 且颜色均一, 没有明显的核壳结构. 用苯硫酚(TP)作为探针分子研究了合金纳米粒子的表面增强拉曼光谱(SERS). 结果表明, SERS强度与合金纳米粒子的组成和尺寸有关. 当纳米粒子粒径一定时, 除Au25Ag75外, 随着金的增加SERS强度增强. Au25Ag75的粒径比Ag小, 导致SERS强度比Ag低. Au50Ag50和Au75Ag25加入TP分子后, 其聚集方式与Au相似, 等离子体共振峰逐渐靠近1064 nm, 金含量较高时, TP的SERS归于聚集体的等离子体共振增强的贡献.     

有序Au/Ag纳米碗阵列的简易制备及其表面增强拉曼散射性能

通过湿法化学合成基于SiO₂胶体晶体的大面积有序Au/Ag纳米碗(Au/AgNB)阵列。首先,在玻璃基板上组装3D SiO₂胶体晶体作为模板。然后,以Au纳米颗粒(AuNP)为种子,通过原位生长法在SiO₂模板上沉积一层Au纳米壳(AuNS)。再通过HCHO还原Ag⁺成Ag⁰,进一步在AuNS表面沉积Ag纳米壳,形成Ag/Au双纳米壳(Ag/AuNS)阵列。最后通过丙烯酸酯改性双向取向聚丙烯(BOPP)膜方便地获得了单层有序反转Ag/AuNB阵列。这种有序Au/AgNB阵列具有更佳的表面增强拉曼散射(SERS)活性,其SERS分析增强因子(AEF)可达2.23×10⁷。     

有序Au/Ag纳米碗阵列的简易制备及其表面增强拉曼散射性能

通过湿法化学合成基于SiO₂胶体晶体的大面积有序Au/Ag纳米碗(Au/AgNB)阵列。首先,在玻璃基板上以3D SiO₂胶体晶体作为模板。然后,在Au纳米颗粒(AuNP)种子的帮助下,通过原位生长方法在模板上沉积一层Au纳米壳(AuNS)。再通过HCHO还原Ag⁺使AuNS表面进一步沉积Ag纳米壳,形成Ag/Au双纳米壳(Ag/AuNS)阵列。通过丙烯酸酯改性双向取向聚丙烯(BOPP)方便地获得了单层有序反转Ag/AuNB阵列。这种有序Au/AgNB阵列具有更佳的表面增强拉曼散射(SERS)活性,其SERS分析增强因子(AEF)可达2.23×10⁷。     

Synthesis of AgcoreAushell bimetallic nanoparticles for immunoassay based on surface-enhanced Raman spectroscopy

Layered core-shell bimetallic silver-gold nanoparticles were prepared by coating Au layers over Ag seeds by a seed-growth method. The composition of Ag100-xAux particles can vary from x=0 to 30. TEM and SEM images clearly show that the bimetallic nanoparticles are of core-shell structure with some pinholes on the surface. Strong surface-enhanced Raman (SER) signals of thiophenol and p-aminothiophenol have been obtained with these colloids. It was found that the SERS activity of aggregated colloids critically depends on the molar ratio of Ag to Au. With the increase of the Au molar fraction, the SERS activity enhances first and then weakens, with the maximal intensity being 10 times stronger than that of Ag colloids. The AgcoreAushell nanoparticles were then labeled with monoclonal antibodies and SERS probes and used for immunoassay analysis. In the proposed system, antibodies immobilized on a solid substrate can interact with the corresponding antigens to form a composite substrate, which can capture reporter-labeled AgcoreAushell nanoparticles modified with the same antibodies. The immunoreaction between the antibodies and antigens was demonstrated by the detection of characteristic Raman bands of the probe molecules. AgcoreAushell bimetallic nanoparticles, as a new SERS active and biocompatible substrate, will be expected to improve the detection sensitivity of immunoassay.     

稳定分散的纳米银溶胶的制备及其表征

Stable aqueous dispersive colloidal Ag nanoparticles were prepared by reducing silver nitrate with sodium borohydride in the presence of 3-mercaptopropionic acid. The formation process of the Ag nanoparticles was investigated by UV-Visible spectroscopy and transmission electron microscopy. The results show that the spherical and rodlike particles and aggregates are formed in the initial stage of the reaction， then the rodlike particles and aggregates are gradually decomposed into small spherical particles， and the final obtained Ag nanoparticles with an average size of 8 nm are in uniform shapes and narrow size distribution， and the colloid remains stable for more than one month， which makes it convenient for use in practice. The presence of capping agent plays an extra role over nanoparticles stabilization and morphology. The presence of capping agent on the surface of Ag nanoparticle is confirmed by the X-ray photoelectron spectroscopy. It is found that Ag nanoparticles are negatively charged in alkaline condition， whereas they are positively charged in acid condition. Electrosteric effect is responsible for their long-term stability.     

Self-assembled metal colloid films: two approaches for preparing new SERS active substrates

In this paper, we propose two new approaches for preparing active substrates for surface-enhanced Raman scattering (SERS). In the first approach (method 1), one transfers AgI nanoparticles capped by negatively charged mercaptoacetic acid from a AgI colloid solution onto a quartz slide and then deoxidizes AgI to Ag nanoparticles on the substrate. The second approach (method 2) deoxidizes AgI to Ag nanoparticles in a colloid solution and then transfers the Ag nanoparticles capped by negatively charged mercaptoacetic acid onto a quartz slide. By transfer of the AgI/Ag nanoparticles from the colloid solutions to the solid substrates, the problem of instability of the colloid solutions can largely be overcome. The films thus prepared by both approaches retain the merits of metal colloid solutions while they discharge their shortcomings. Accordingly, the obtained Ag particle films are very suitable as SERS active substrates. SERS active substrates with different coverages can be formed in a layer-by-layer electrostatic assembly by exposing positively charged surfaces to the colloid solutions containing oppositely charged AgI/Ag nanoparticles. The SERS active substrates fabricated by the two novel methods have been characterized by means of atomic force microscopy (AFM) and ultraviolet-visible (UV-vis) spectroscopy. The results of AFM and UV-vis spectroscopy show that the Ag nanoparticles grow with the increase in the number of coverage and that most of them remain isolated even at high coverages. Consequently, the surface optical properties are dominated by the absorption due to the isolated Ag nanoparticles. The relationship between SERS intensity and surface morphology of the new active substrates has been investigated for Rhodamine 6G (R6G) adsorbed on them. It has been found that the SERS enhancement depends on the size and aggregation of the Ag particles on the substrates. Especially, we can obtain a stronger SERS signal from the substrate prepared by method 1, implying that for the metal nanoparticles capped with stabilizer molecules such as mercaptoacetic acid, the in situ deoxidization in the film is of great use in preparing SERS active substrates. Furthermore, we have found that the addition of Cl- into the AgI colloid solution changes the surface morphology of the SERS active substrates and favors stronger SERS enhancement.     

Pillar[5]arene‐Mediated Synthesis of Gold Nanoparticles: Size Control and Sensing Capabilities

We present a simple procedure for the synthesis of quasi‐spherical Au nanoparticles in a wide size range mediated by macrocyclic host molecules, ammonium pillar[5]arene (AP[5]A). The strategy is based on a seeded growth process in which the water‐soluble pillar[5]arene undergoes complexation of the Au salt through the ammonium groups, thereby avoiding Au nucleation, while acting as a stabilizer. The presence of the pillar[5]arene onto the Au nanoparticle particle surface is demonstrated by surface‐enhanced Raman scattering (SERS) spectroscopy, and the most probable conformation of the molecule when adsorbed on the Au nanoparticles surface is suggested on the basis of theoretical calculations. In addition, we analyze the host–guest interactions of the AP[5]A with 2‐naphthoic acid (2NA) by using ¹H NMR spectroscopy and the results are compared with theoretical calculations. Finally, the promising synergetic effects of combining supramolecular chemistry and metal nanoparticles are demonstrated through SERS detection in water of 2NA and a polycyclic aromatic hydrocarbon, pyrene (PYR).     

Silver Coated Platinum Core–Shell Nanostructures on Etched Si Nanowires: Atomic Layer Deposition (ALD) Processing and Application in SERS

A new method to prepare plasmonically active noble metal nanostructures on large surface area silicon nanowires (SiNWs) mediated by atomic layer deposition (ALD) technology has successfully been demonstrated for applications of surface‐enhanced Raman spectroscopy (SERS)‐based sensing. As host material for the plasmonically active nanostructures we use dense single‐crystalline SiNWs with diameters of less than 100 nm as obtained by a wet chemical etching method based on silver nitrate and hydrofluoric acid solutions. The SERS active metal nanoparticles/islands are made from silver (Ag) shells as deposited by autometallography on the core nanoislands made from platinum (Pt) that can easily be deposited by ALD in the form of nanoislands covering the SiNW surfaces in a controlled way. The density of the plasmonically inactive Pt islands as well as the thickness of noble metal Ag shell are two key factors determining the magnitude of the SERS signal enhancement and sensitivity of detection. The optimized Ag coated Pt islands on SiNWs exhibit great potential for ultrasensitive molecular sensing in terms of high SERS signal enhancement ability, good stability and reproducibility. The plasmonic activity of the core‐shell Pt//Ag system that will be experimentally realized in this paper as an example was demonstrated in numerical finite element simulations as well as experimentally in Raman measurements of SERS activity of a highly diluted model dye molecule. The morphology and structure of the core‐shell Pt//Ag nanoparticles on SiNW surfaces were investigated by scanning‐ and transmission electron microscopy. Optimized core–shell nanoparticle geometries for maximum Raman signal enhancement is discussed essentially based on the finite element modeling.     

Surface enhanced Raman scattering investigation of the halide anion effect on the adsorption of 1,2,3-triazole on silver and gold colloidal nanoparticles

The halide anion effect on the adsorption of 1,2,3-triazole on Ag and Au colloidal nanoparticles has been investigated by means of surface enhanced Raman scattering (SERS), UV-visible absorption spectroscopy, and scanning electron microscopy. To interpret the SERS spectra, the vibrational spectra of 1,2,3-triazole were assigned with the help of density functional theoretical (DFT) calculations of the two tautomers of 1,2,3-triazole, both free and bound to Ag and Au adatoms. Upon addition of halide anions, both tautomers interact with the Ag surface through one nitrogen atom. Analogous behavior is observed in the case of basified Au colloids, whereas at the usual pH of these hydrosols (approximately 6) the adsorption of 1,2,3-triazole is the same of that observed in halide-free colloids.     

金核银壳纳米粒子薄膜的制备及SERS活性研究

采用柠檬酸化学还原法制备金溶胶, 通过自组装技术在石英片表面制备金纳米粒子薄膜, 在银增强剂混合溶液中反应获得金核银壳纳米粒子薄膜. 用紫外-可见吸收光谱仪和原子力显微镜(AFM)研究了不同条件下制备的金核银壳纳米粒子薄膜的光谱特性和表面形貌, 并以结晶紫为探针分子测量了金核银壳纳米粒子薄膜的表面增强拉曼光谱(SERS). 结果表明, 金纳米粒子薄膜的分布、银增强剂反应时间的长短对金核银壳纳米粒子薄膜的形成均有重要影响. 制备过程中, 可以通过控制反应条件获得一定粒径的、具有良好表面增强拉曼散射活性的金核银壳纳米粒子薄膜.     

Self‐Assembled Au Nanoparticles as Substrates for Surface‐Enhanced Vibrational Spectroscopy: Optimization and Electrochemical Stability

Three‐dimensional nanostructured metallic substrates for enhanced vibrational spectroscopy are fabricated by self‐assembly. Nanostructures consisting of one to 20 depositions of 13 nm‐diameter Au nanoparticles (NPs) on Au films are prepared and characterized by means of AFM and UV/Vis reflection–absorption spectroscopy. Surface‐enhanced polarization modulation infrared reflection–absorption spectroscopy (PM‐IRRAS) is observed from Au NPs modified by the probe molecule 4‐hydroxythiophenol. The limitation of this kind of substrate for surface‐enhanced PM‐IRRAS is discussed. The surface‐enhanced Raman scattering (SERS) from the same probe molecule is also observed and the effect of the number of Au‐NP depositions on the SERS efficiency is studied. The SERS signal from the probe molecule maximizes after 11 Au‐NP depositions, and the absolute SERS intensities from different batches are reproducible within 20 %. In situ electrochemical SERS measurements show that these substrates are stable within the potential window between ?800 and +200 mV (vs. Ag/AgCl/sat. Cl^?).     

Raman scattering of 4-aminobenzenethiol sandwiched between Ag/Au nanoparticle and macroscopically smooth Au substrate

Raman scattering measurements were conducted for a 4-aminobenzenethiol (4-ABT) monolayer assembled on a macroscopically smooth Au substrate. Although no peak was detected at the beginning, Raman peaks were distinctly observed by attaching Ag or Au nanoparticles onto the 4-ABT monolayer (Ag(Au)@4-ABT/Au(flat)). Considering the fact that no Raman signal is observed when Ag (Au) nanoparticles are adsorbed on a (4-aminophenyl)silane monolayer assembled on a silicon wafer, the Raman spectrum observed for Ag(Au)@4-ABT/Au(flat) must be a surface-enhanced Raman scattering (SERS) spectrum, derived from the electromagnetic coupling of the localized surface plasmon of Ag (Au) nanoparticles with the surface plasmon polariton of the underneath Au metal. The electromagnetic coupling responsible for SERS appeared to be governed more by the bulk Au substrate than the sparsely distributed Ag or Au nanoparticles. The chemical enhancement appeared on the other hand to be derived more from the formation of Au-S bonds than any charge-transfer interaction between the protonated amine group and the Au or Ag nanoparticles. The enhancement factors derived from the attachment of a single Ag or Au nanoparticle onto 4-ABT on Au were estimated to be as large as 8.3 x 10(5) and 5.0 x 10(5), respectively, (for the ring 3 band (b(2)) near 1390 cm(-1)) in which a factor of approximately 10(2) was presumed to be due to the chemical effect, with the remaining contributed by the electromagnetic effect.     

铁氧化物/金磁性核壳纳米粒子的制备及其富集与SERS研究

本文用种子生长法制备铁氧化物/金磁性核壳纳米粒子, 并利用SERS对其磁场靶向性进行了检测.     

A rapid and simple chemical method for the preparation of Ag colloids for surface-enhanced Raman spectroscopy using the Ag mirror reaction

Colloidal silver (Ag) nanoparticles (AgNP) have been widely used for surface-enhanced Raman spectroscopy (SERS) applications. We report a simple, rapid and effective method to prepare AgNP colloids for SERS using the classic organic chemistry Ag mirror reaction with Tollens’ reagent. The AgNP colloid prepared with this process was characterized using SEM, and the reaction conditions further optimized using SERS measurements. It was found that Ag mirror reaction conditions that included 20 mM AgNO₃, 5 min reaction time, and 0.5 M glucose produced AgNP colloids with an average size of 319.1 nm (s.d ± 128.1). These AgNP colloids exhibited a significant SERS response when adenine was used as the reporter molecule. The usefulness of these new AgNP colloids was demonstrated by detecting the nucleotides adenosine 5′-mono-phosphate (AMP), guanosine 5′-monophosphate (GMP), cytidine 5′-monophosphate (CMP), and uridine 5′-monophosphate (UMP). A detection limit of 500 nM for AMP was achieved with the as-prepared AgNP colloid. The bacterium Mycoplasma pneumoniae was also easily detected in laboratory culture with these SERS substrates. These findings attest to the applicability of this AgNP colloid for the sensitive and specific detection of both small biomolecules and microorganisms.     

Hematite spindles with optical functionalities: growth of gold nanoshells and assembly of gold nanorods

The layer-by-layer (LBL) assembly method, combined with the seeded growth technique, have been used to deposit gold shells on the surface of hematite (alpha-Fe(2)O(3)) spindles. While the LBL method yields dense coatings of preformed Au nanoparticles, when AuCl(-)(4) ions are further reduced by a mild reducing agent, thicker, rough nanostructured shells can be grown. The deposition process was monitored by TEM and UV-visible spectroscopy, demonstrating a gradual change in the optical features of the colloids as the surface is more densely covered. The particles so-prepared can find useful applications in cancer therapy and as SERS substrates. Additionally, we show that Au nanorods can be assembled on hematite spindles, providing a flexible way to tune the optical properties of the resulting composite colloids.