SHINERS and plasmonic properties of Au Core SiO2 shell nanoparticles with optimal core size and shell thickness

Shell‐isolated nanoparticles (NPs)‐enhanced Raman spectroscopy (SHINERS) can be potentially applied to virtually any substrate type and morphology. How to take a step forward to prepare SHINERS NPs (SHINs) with superior performance is critical for the practical applications of surface‐enhanced Raman scattering (SERS) in the breadth and depth. Here, we present a method to obtain 120 nm diameter gold NPs coated with ultrathin silica shells (1–4 nm). The silica shell can be controlled growth through carefully tuning a series of parameters, such as amount of 3‐aminopropyl triethoxysilane used, pH, reaction time, and reaction temperature. We compare the enhancement factor of the obtained 120 nm Au with a 4 nm silica shell NPs to the 55 nm Au with a 4 nm silica shell NPs, and the activity of a 120 nm SHINs is nearly 24 times that the 55 nm SHIN from a single particle view. We also compare the enhancement factor of 1 nm silica shell Au@SiO₂ NPs with the bare Au NPs. The enhancement factor of 1 nm silica shell Au@SiO₂ NPs was found to be about twice that of the bare particles. For a deeper understanding of the source of the giant enhanced electrical field of the 1 nm silica shell Au@SiO₂ NPs, we study the plasmonic property of single 1 nm silica shell Au@SiO₂ NP on a gold film substrate through correlation of the structure of single NP using SEM with its SPR spectroscopy. We find that the multipolar interaction between the single Au@SiO₂ NP and gold film substrate is important for the SERS. Our studies on the performance of 120 nm SHINs and the plasmonic property of these particles can significantly expand the applications of SHINERS technique and improve the understanding of physical nature of SHINs. Copyright © 2013 John Wiley & Sons, Ltd.     

SERS of the anti‐inflammatory drug piroxicam adsorbed on the surface of silver or gold colloids as nanocarrier model

Piroxicam is a non‐steroidal anti‐inflammatory drug actually used with limitations because of serious side effects. It is poorly soluble in pure water and exhibit a minimum of four conformers according to the pH conditions of the solution, but not all of them are medically active. In this study, we present, firstly, the Raman characterization of piroxicam in different organic solvents (dimethyl sulfoxide, 1,4‐dioxane, ethanol, 1‐propanol). These results have permitted us to analyze surface‐enhance Raman scattering spectra of piroxicam adsorbed on gold or silver nanoparticles surface at several pHs (1, 2, 4, and 7), imitating the environment of the drug in the body, either in the gastrointestinal tract or in healthy and disease tissues. Results indicate that, below pH = 7, piroxicam is mainly in the zwitterionic conformer, and molecules are oriented parallel to the noble metal surface; however at pH ≥ 7, the main specie detected is the anionic one, differently oriented with respect to the nanoparticle surface. The metal‐piroxicam systems here characterized by surface‐enhance Raman scattering spectroscopy could constitute nanocarriers in future projects of transporting and releasing of the drug in the body. Copyright © 2015 John Wiley & Sons, Ltd.     

Functionalization of gold and silver nanoparticles with diphenyl dichalcogenides probed by surface enhanced Raman scattering

This paper describes a surface‐enhanced Raman scattering (SERS) systematic investigation regarding the functionalization of gold (Au) and silver (Ag) nanoparticles with diphenyl dichalcogenides, i.e. diphenyl disulfide, diphenyl diselenide, and diphenyl ditelluride. Our results showed that, in all cases, functionalization took place with the cleavage of the chalcogen–chalcogen bond on the surface of the metal. According to our density functional theory calculations, the molecules assumed a tilted orientation with respect to the metal surface for both Au and Ag, in which the angle of the phenyl ring relative to the metallic surface decreased as the mass of the chalcogen atom increased. The detected differences in the ordinary Raman and SERS spectra were assigned to the distinct stretching frequencies of the carbon–chalcogen bond and its relative contribution to the ring vibrational modes. In addition, the SERS spectra showed that there was no significant interaction between the phenyl ring and the surface, in agreement with the tilted orientation observed from our density functional theory calculations. The results described herein indicate that diphenyl dichalcogenides can be successfully employed as starting materials for the functionalization of Au nanoparticles with organosulfur, organoselenium, and organotellurium compounds. On the other hand, diphenyl disulfide and diphenyl diselenide could be employed for the functionalization of Ag nanoparticles, while the partial oxidation of the organotellurium unit could be detected on the Ag surface. Copyright © 2011 John Wiley & Sons, Ltd.     

Spectral characterization and intracellular detection of Surface‐Enhanced Raman Scattering (SERS)‐encoded plasmonic gold nanostars

Plasmonic gold nanostars offer a new platform for surface‐enhanced Raman scattering (SERS). However, due to the presence of organic surfactant on the nanoparticles, SERS characterization and application of nanostar ensembles in solution have been challenging. Here, we applied our newly developed surfactant‐free nanostars for SERS characterization and application. The SERS enhancement factors (EF) of silver spheres, gold spheres and nanostars of similar sizes and concentration were compared. Under 785 nm excitation, nanostars and silver spheres have similar EF, and both are much stronger than gold spheres. Having plasmon matching the incident energy and multiple ‘hot spots’ on the branches bring forth strong SERS response without the need to aggregate. Intracellular detection of silica‐coated SERS‐encoded nanostars was also demonstrated in breast cancer cells. The non‐aggregated field enhancement makes the gold nanostar ensemble a promising agent for SERS bioapplications. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis of different gold nanostructures by solar radiation and their SERS spectroscopy

In this article, a simple and novel photochemical synthesis of different gold nanostructures is proposed using solar radiation. This method is rapid, convenient and of low cost, and can be performed under ambient conditions. By adjusting the concentration of sodium acetate (NaAc), different morphologies of the products can be easily obtained. Without NaAc, the products obtained are mainly polyhedral gold particles; lower concentration of NaAc (0.05 and 0.1 M) accelerates the formation of flowerlike gold nanostructures; while higher concentration of NaAc (0.5 M) facilitates the formation of a variety of gold nanowires and nanobelts. It is found that the morphology change of gold nanaostructures is the result of the synergistic effect of poly(diallyl dimethylammonium) chloride (PDDA), Ac⁻ ions, and the pH value. In addition, the different gold nanostructures thus obtained were used as substrates for surface‐enhanced Raman scattering (SERS) with p‐aminothiophenol (p‐ATP) as the probe molecule. In comparison, the flowerlike gold nanostructures show stronger SERS effect than the other gold nanostructures, which is associated with their unique geometrical shapes providing highly localized electromagnetic (EM) field for the optical enhancement to the probe molecules. These gold nanostructures, with different geometrical shapes, might have potential applications in the areas of photonics, optoelectronics and optical sensing. Copyright © 2009 John Wiley & Sons, Ltd.     

Site‐specific deposition of Ag nanoparticles on ZnO nanorod arrays via galvanic reduction and their SERS applications

A controllable heterostructure consisting of ZnO nanorod arrays with attached Ag nanoparticles at only one end has been synthesized via a facile and convenient galvanic reduction method. Scanning electron microscopic images of these nanostructures showed good selectivity of Ag deposition on the tip of ZnO nanorod arrays. The formation of these regular Ag ZnO heterogeneous nanorod arrays can be explained by a localization of the electrons at the ends of the ZnO nanorods after the electron transfer step. By tuning the reaction time and the concentration of silver nitrate, the density of Ag nanoparticles on the tip of ZnO nanorods can be well controlled. Owing to the introduction of Ag nanoparticles with different densities, the resulting Ag ZnO heterogeneous nanorod arrays have been proved to be a versatile substrate for surface‐enhanced Raman scattering not only for common organic molecules but also for label‐free protein detection. Copyright © 2009 John Wiley & Sons, Ltd.     

SERS studies of isolated and agglomerated gold nanoparticles functionalized with a dicarboxybipyridine‐trimercaptotriazine‐ruthenium dye

A dicarboxybipyridine‐trimercaptotriazine ruthenium complex, primarily designed for dye solar cells, has been successfully employed for generating electrostatically stabilized gold colloids, because of its high negative charge and capability of binding to gold nanoparticles via the sulfur groups. Surprisingly, a strong surface‐enhanced Raman scattering enhancement has been observed for the isolated nanoparticles, exceeding those recorded after inducing agglomeration. Such unusual response has been ascribed to the predominant contribution of the charge‐transfer and resonance Raman mechanisms, more than compensating for the lack of the local hot spots, in relation to the agglomerated systems. Copyright © 2014 John Wiley & Sons, Ltd.     

In situ nucleation and growth of silver nanoparticles in membrane materials: a controllable roughened SERS substrate with high reproducibility

A controllable roughened silver surface with high surface‐enhanced Raman scattering (SERS) activity and high reproducibility has been developed in this study. This silver surface was prepared by silver nucleation in polyelectrolyte multilayers (PEMs) and silver‐enlarged growth. First, the small Ag nuclei were synthesized by NaBH₄ in situ reduction of Ag ions on a surface of PEMs. Then the small Ag nuclei formed were effectively enlarged by using a mixture of commercially available reagents named Li Silver . The optical properties and morphologies of the silver substrates have been investigated by ultraviolet–visible (UV–vis) spectroscopy and atomic force microscopy (AFM). The UV–vis and AFM results revealed that the small Ag nuclei separately appeared on the PEMs after NaBH₄ in situ reduction. The size of the enlarged Ag nanoparticles can be easily controlled with the immersing cycle in Li Silver. 4‐Mercaptopyridine (4‐MPY) and Rhodamine 6G (R6G) have been used as Raman probes to evaluate the properties of the new SERS substrates. It has been found that the enhancement factor of R6G reached ∼10⁹ after treatment in Li Silver. Reproducibility has been investigated using the SERS signal intensity at 1094 cm⁻¹ of 4‐MPY. Signals collected over multiple spots within the same substrate resulted in a relative standard deviation (RSD) of 6.38%, while an RSD of 10.33% was measured in signals collected from different substrates. Copyright © 2008 John Wiley & Sons, Ltd.     

Adsorption of purpald SAMs on silver and gold electrodes: a Raman mapping study

The adsorption modes of 4‐amino‐3‐hydrazino‐5‐mercapto‐1,2,4‐trizole (purpald) self‐assembled monolayers (SAMs) formed on SERS‐active silver and gold electrodes were comparatively studied using surface‐enhanced Raman scattering (SERS), and the self‐assembling procedures were investigated by the Raman mapping technique. Purpald SAMs adopted a titled orientation with S, N2 atoms anchoring to the silver electrode and the  N7H₂ close to the surface, whereas purpald stood up on the gold electrode through S, N5 atoms and with  N8H₂ adjacent to the surface. The density functional theory (DFT) at the level of B3LYP was performed to help explain their different adsorption behaviors on the silver and gold electrodes. Copyright © 2006 John Wiley & Sons, Ltd.     

金纳米棒核/贵金属壳杂化纳米结构的可控制备和性质调控

贵金属纳米颗粒由于其独特的光学及催化性能引起了人们的广泛关注,而这些性能与纳米颗粒的尺寸、形貌、结构组成等密切相关.目前如何有意识地控制晶体生长过程,以得到人们需要的纳米结构和组成,仍具有相当大的挑战性.文章重点介绍了利用具有特定形貌和晶面组成的金纳米棒(Au nanorods)作为种子,借助形成核/壳结构,诱导了Ag, Pd, Pt棒状纳米结构的形成,并实现了对杂化纳米结构光学和催化性能的调控,进一步扩展了贵金属纳米结构的应用范围.作者的研究结果表明,形成杂化纳米结构是性能调控的一种有效方式.     

Preparation and characterization of core/shell particles with siloxane in the shell

The core/shell particles consisting of polystyrene core and 3-(methacryloxypropyl)-trimethoxysilane (MPS) shell were prepared in the present study by successive seeding polymerization under kinetically controlled conditions and were characterized by particle size analyser, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The TEM image indicated that the particles containing organic siloxane presented an evident core/shell structure. Additionally, the study of XPS also revealed that MPS could be grafted onto the surface of polystyrene microspheres and the atomic ratio of C/Si on the surface of the core/shell particles (MPS-40) was very close to the ratio of C/Si in the molecule of MPS. The surface properties of the films produced from the core/shell particles were also investigated by the static contact angle method. Compared with the homopolymer of PS, the core/shell particles were more effective to create hydrophobic surface, so, the introduction of MPS was capable of obvious increase in water repellency.     

金纳米棒核/贵金属壳杂化纳米结构的可控制备和性质调控

贵金属纳米颗粒由于其独特的光学及催化性能引起了人们的广泛关注,而这些性能与纳米颗粒的尺寸、形貌、结构组成等密切相关.目前如何有意识地控制晶体生长过程,以得到人们需要的纳米结构和组成,仍具有相当大的挑战性.文章重点介绍了利用具有特定形貌和晶面组成的金纳米棒（Au nanorods）作为种子,借助形成核/壳结构,诱导了Ag...     

Template synthesis of nanostructured silica with hollow core and mesoporous shell structures

Silica capsules with hollow macroporous core–mesoporous shell (HCMS) were synthesized through template-assisted replication of submicrometer-size polystyrene spheres as templates. The silica mesoporous shell exhibited highly ordered hexagonal structure as confirmed by X-ray diffraction pattern and TEM image. The pore diameter and BET surface area of this sample were found to be 2.1 nm and 1387 m²/g, respectively.     

Tailoring the optical and hydrophobic property of zinc oxide nanorod by coating with amorphous graphene

Zinc oxide (ZnO) nanorods were synthesized at room temperature on potassium permanganate activated silicon and glass substrate by simple chemical method using zinc acetate as precursor.To modify the surface energy of the as prepared ZnO thin films the samples were coated with amorphous graphene (a-G) synthesized by un-zipping of chemically synthesized amorphous carbon nanotubes (a-CNTs). All the pure and coated samples were characterized by x-ray diffraction, field emission scanning electron microscope, Raman spectroscopy, and Fourier transformed infrared spectroscopy. The roughness analysis of the as prepared samples was done by atomic force microscopic analysis. The detail optical properties of all the samples were studied with the help of a UV-Visible spectrophotometer.The surface energy of the as prepared pure and coated samples was calculated by measuring the contact angle of two different liquids. It is seen that the water repellence of ZnO nanorods got increased after they are being coated with a-Gs. Also even after UV irradiation the contact angle remain same unlike the case for the uncoated sample where the contact angle gets decreased significantly after UV irradiation. Existing Cassie-Wenzel model has been employed along with the Owen's approach to determine the different components of surface energy.     

Cu/C核/壳纳米结构的气相合成、形成机理及其光学性能研究

采用乙酰丙酮铜为原料, 通过化学气相沉积大批量制备出Cu/C核/壳纳米颗粒和纳米线. 研究结果表明, 通过控制沉积温度可对Cu/C核/壳纳米材料的形貌和结构进行很好的控制. 比如, 沉积温度为400 ℃时可获得直径约200 nm的Cu/C核/壳纳米线, 沉积温度为450 ℃ 时可获得直径约200 nm的Cu/C核/壳纳米颗粒和纳米棒的混合产物, 沉积温度为600 ℃时可获得直径约22 nm的Cu/C核/壳纳米颗粒. 获得的Cu/C核/壳纳米结构是由一个新颖的凝聚机理形成的, 而这种机理不同于著名的溶解-析出机理. 紫外-可见光谱和荧光光谱分析结果表明: Cu/C核/壳纳米线和纳米颗粒均在225 nm处出现Cu的吸收峰, 同时在620 和616 nm处分别出现了纳米线和纳米颗粒的表面等离子共振吸收峰. Cu/C核/壳纳米线在312 和348 nm处、 Cu/C核/壳纳米颗粒在304 和345 nm处出现荧光发射谱峰. 关键词： Cu/C核/壳结构 纳米线 纳米颗粒 光学性能     

Au@SiO2 core/shell nanoparticle assemblage used for highly sensitive SERS‐based determination of glucose and uric acid

The use of Au@SiO₂ core/shell nanoparticle (NP) assemblage with highly sensitive surface‐enhanced Raman scattering (SERS) was investigated for the determination of glucose and uric acid in this study. Rhodamine 6G dye molecules were used to evaluate the SERS enhancement factor for the synthesized Au@SiO₂ core/shell NPs with various silica shell thicknesses. The enhancement of SERS signal from Rhodamine 6G was found to increase with a decrease in the shell thickness. The core/shell assemblage with silica layer of 1–2 nm over a Au NP of ~36 nm showed the highest SERS signal. Our results show that the SERS technique is able to detect glucose and uric acid within wide concentration ranges, i.e. 20 ng/dL to 20 mg/dL (10⁻¹²–10⁻³ M) and 16.8 ng/dL to 2.9 mg/dL (10⁻¹¹–1.72 × 10⁻⁴ M), respectively, with associated lower detection limits of ~20 ng/dL (~1.0 × 10⁻¹² M) and ~16.8 ng/dL (~1.0 × 10⁻¹¹ M). Our work offers a low‐cost route to the fabrication of agile sensing devices applicable to the monitoring of disease progression. Copyright © 2013 John Wiley & Sons, Ltd.     

Preparation and property of polyvinyl alcohol-based film embedded with gold nanoparticles

Gold nanoparticles were prepared by a simple heat-treated method using polyvinyl alcohol (PVA) as reducing and stabilizing agent in this article. UV/Vis spectroscopy was used to monitor the preparation. The formation of a sharp band at ~530 nm in the UV/Vis spectra and morphological characters revealed by transmission electron microscopy indicated the generation of Au nanoparticles. The PVA film embedded with Au nanoparticles was prepared by flow casting method and characterized by thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction, Fourier transform infrared spectra, and X-ray photoelectron spectroscopy. The results showed that Au nanoparticles embedded in PVA film can improve the thermal stability of the film under investigation, leading to interesting technological applications.     

Mechanical property and deformation mechanism of gold nanowire with non-uniform distribution of twinned boundaries:A molecular dynamics simulation study

The mechanical property and deformation mechanism of twinned gold nanowire with non-uniform distribution of twinned boundaries(TBs) are studied by the molecular dynamics(MD) method. It is found that the twin boundary spacing(TBS) has a great effect on the strength and plasticity of the nanowires with uniform distribution of TBs. And the strength enhances with the decrease of TBS, while its plasticity declines. For the nanowires with non-uniform distribution of TBs, the differences in distribution among different TBSs have little effect on the Young's modulus or strength, and the compromise in strength appears. But the differences have a remarkable effect on the plasticity of twinned gold nanowire. The twinned gold nanowire with higher local symmetry ratio has better plasticity. The initial dislocations always form in the largest TBS and the fracture always appears at or near the twin boundaries adjacent to the smallest TBS. Some simulation results are consistent with the experimental results.