Janus Multicolored Photonic Crystal Beads for Real‐Time Magnetic Responsive Patterns

Photonic Janus particles that can change colors in different stimuli have shown great promise in various applications, such as optical probes, catalyst supports, sensors, and display materials. However, it remains a challenge to produce Janus structural colored particles with a simple method. Inspired from ecsenius bicolors, a facile preparation of Janus structural colored beads (JSCBs) using sub‐micrometer‐sized colloidal particles and magnetic nanoparticles composed of Fe₃O₄ is established. A mixed emulsion is prepared by monodispersed colloidal particles and magnetic nanoparticles and initiator of PDMS precursor. Subsequent self‐assembly of the emulsion in the room temperature environment provides two different structural colors, thanks to the gravity deposition of colloidal particles and Fe₃O₄ nanoparticles. The photonic bandgap of JSCBs can be precisely controlled with varying size of monodispersed colloidal nanoparticles, and the high optical quality and mechanical strength of the structural colored face are attributed to the existence of PDMS. In the presence of a magnet, the JSCBs can change their orientation simultaneously between two different structural colors. Moreover, the JSCBs are capable of encoding and angle‐independent displaying, which are crucial to their applications in anticounterfeiting, information coding, and pattern display.     

Gold and Silver Nanomaterial‐Based Optical Sensing Systems

Gold and silver nanomaterials (NMs) such as nanoparticles (NPs) and nanoclusters (NCs) possessing interesting optical properties have become popular sensing materials. With strong surface plasmon resonance (SPR) absorption, extraordinary stability, ease in preparation, conjugation, and biocompatibility, Au NPs are employed to develop sensitive and selective sensing systems for a variety of analytes. However, small sizes of Au and Ag NCs with interesting photoluminescence (PL) properties are used in many PL‐based sensing systems for the detection of important analytes. In addition, many bimetallic AuM NMs possessing strong catalytic activity are used to develop highly sensitive fluorescent sensors. This review article is categorized in four sections based on the NMs used in the sensing systems, including Au NPs, bimetallic AuM NMs, Au NCs, and DNA–Ag NCs. In each section, synthetic strategies and optical properties of the NMs are provided briefly, followed by emphasis on their analytical applications in the detection of small molecules, metal ions, DNA, proteins, and cells. Current challenges and future prospects of these NMs‐based sensing systems will be addressed.     

Sonochemical preparation of composite nanoparticles of Au/gamma-Fe2O3 and magnetic separation of glutathione

We prepared Au/gamma-Fe2O3 composite nanoparticles by sonochemically reducing Au(III) ions employing no stabilizer in the aqueous solution to form stable Au nanoparticles and allowing them to attach onto the surface of gamma-Fe2O3 particles with an average size of 21 nm. Size of the formed Au nanoparticle depended on the initial concentration of Au(III) ions. The number of the Au nanoparticles, supported on each gamma-Fe2O3 particle was controlled by changing the relative amounts of Au(III) ions and gamma-Fe2O3 particles. The composite nanoparticles exhibited a high affinity with glutathione, a tripeptide with mercapto group so that separation and manipulation of glutathione in aqueous solutions could be performed by application of external magnetic field. Because the surfaces of the Au nanoparticles were not shielded by any stabilizers, or naked, sonochemically prepared Au/gamma-Fe2O3 composite nanoparticles seemed to show stronger affinity to the glutathione than those by the radiochemical method.     

1-Hexadecylamine as both reducing agent and stabilizer to synthesize Au and Ag nanoparticles and their SERS application

1-Hexadecylamine (HDA)-capped Au and Ag nanoparticles (NPs) have been successfully prepared by a one-pot solution growth method. The HDA is used as both reducing agent and stabilizer in the synthetic process is favorable for investigating the capping mechanism of Au and Ag NPs’ surface. The growth process and characterization of Au and Ag NPs are determined by Ultraviolet–visible (UV–vis) spectroscopy, transmission electron microscopy (TEM), and X-ray diffraction (XRD). Experimental results demonstrate that the HDA-capped Au and Ag NPs are highly crystalline and have good optical properties. Furthermore, surface-enhanced Raman scattering (SERS) spectra of 2-thionaphthol are obtained on the Au and Ag NPs modified glass surface, respectively, indicating that the as-synthesized noble metal NPs have potentially high sensitive optical detection application.     

Fabrication of NIR‐Excitable SERS‐Active Composite Particles Composed of Densely Packed Au Nanoparticles on Polymer Microparticles

A simple fabrication method is demonstrated for surface‐enhanced Raman scattering (SERS)‐active plasmonic nanoballs, which consisted of Au nanoparticles (NPs) and core–shell polystyrene and amino‐terminated poly(butadiene) particles, by heterocoagulation and Au NP diffusion. The amount of Au NPs introduced into the core–shell particles increases with the concentration of Au NPs added to the aqueous dispersion of the core–shell particles. When the amount of Au NPs increases, closely packed, three‐dimensionally arranged and close‐packed Au NPs arrays are formed in the shells. Strong SERS signals from para‐mercaptophenol adsorbed onto composite particles with multilayered Au NPs arrays are obtained by near‐infrared (NIR) light illumination.     

Rapid synthesize of gold nanoparticles by microwave irradiation method and its application as an optical limiting material

We present rapid synthesis of gold nanoparticles by microwave irradiation method. Sample with average particle size 7.7 nm is obtained from TEM. Linear and nonlinear optical studies of the prepared samples are discussed. Reverse saturable absorption (RSA) at longitudinal surface plasmon resonance (SPR) in gold nanoparticles (Au NPs) have been observed using Z-scan and transient absorption techniques with 532 nm laser pulses. Such RSA behavior makes Au NPs an ideal candidate for optical limiting applications.     

Controlled synthesis and biomolecular probe application of gold nanoparticles

In addition to their optical properties, the ability of gold nanoparticles (Au NPs) to generate table immobilization of biomolecules, whilst retaining their bioactivities is a major advantage to apply them as biosensors. Optical biosensors using Au NPs are simple, fast and reliable and, recently, they have been moving from laboratory study to the point of practical use. The optical properties of Au NPs strongly depend on their size, shape, degree of aggregation and the functional groups on their surface. Rapid advances in the field of nanotechnology offer us a great opportunity to develop the controllable synthesis and modification of Au NPs as well as to study on their properties and applications. The size-controlled growth of Au NPs requires the isotropic growth on the surface of Au nuclei whereas anisotropic growth will induce the formation of Au NPs of varying shape. Functionalized Au NPs provide sensitive and selective biosensors for the detection of many targets, including metal ions, small organic compounds, protein, DNA, RNA and cell based on their optical, electrical or electrochemical signals. In this review, we will discuss the size- and shape-controlled growth and functionalization of Au NPs to obtain Au nanoprobes. The basis of the optical detection of Au nanoprobes and their applications in nucleic acid, protein detection and cell imaging are also introduced.     

High–Yield Production of Uniform Gold Nanoparticles with Sizes from 31 to 577 nm via One‐Pot Seeded Growth and Size‐Dependent SERS Property

In this work, uniform, quasi‐spherical gold nanoparticles (Au NPs) with sizes of 31–577 nm are prepared via one‐pot seeded growth with the aid of tris‐base (TB). Distinct from the seeded growth methods available in literature, the present method can be simply implemented by subsequently adding the aqueous dispersion of the 17 nm Au‐NP seeds and the aqueous solution of HAuCl₄ into the boiling aqueous TB solution. It is found that at the optimal pH range, the sizes of the final Au NPs and their concentrations are simply controlled by either the particle number of the Au seed dispersion or the concentration of the HAuCl₄ solution, while the latter enables us to produce large Au NPs at very high concentration. Moreover, as‐prepared Au NPs of various sizes are coated on glass substrates to test their surface‐enhanced Raman scattering (SERS) activities by using 4‐aminothiophenol (4‐ATP) molecules as probes, which exhibit “volcano type” dependence on the Au NP sizes at fixed excitation wavelength. Furthermore, the Au NPs with sizes of ≈97 and 408 nm exhibit the largest SERS enhancement at the excitation wavelength of 633 and 785 nm, respectively.     

Design of Enhanced Catalysts by Coupling of Noble Metals (Au,Ag) with Semiconductor SnO2 for Catalytic Reduction of 4‐Nitrophenol

The reduction of 4‐nitrophenol (Nip) into 4‐aminophenol (Amp) by NaBH₄, which is catalyzed by both binary and ternary yolk–shell noble‐metal/SnO₂ heterostructures, is reported. The binary heterostructures contain individual Au or Ag nanoparticles (NPs) and the ternary heterostructures contain both Au and Ag NPs. The Au@SnO₂ yolk–shell NPs are synthesized via a silica seeds‐mediated hydrothermal method. Subsequently, the Au@SnO₂@Ag and Au@SnO₂@Au yolk–shell–shell (YSS) NPs are synthesized, whereby SnO₂ is located between the Au and Ag NPs. The morphology, composition, and optical properties of the as‐prepared samples are analyzed. For the binary heterostructures, the rate of the reduction reaction increases with decreasing particle size. The catalytic results demonstrate the synergistic effect of Au and Ag in the ternary metal–semiconductor heterostructures, which is beneficial to the catalytic reduction of Nip into Amp. Both the binary and ternary heterostructures exhibit significantly better catalytic performances than the corresponding bare Au and Ag NPs. It is envisaged that the current synthesized strategy will promote further interest in the field of bimetal NP‐based catalysis.     

Adjustable surface plasmon resonance with Au,Ag, and Ag@Au core-shell nanoparticles

We report an experimental study on the synthesis of metal nanoparticles （NPs） with adjustable optical density based on surface plasmon resonance （SPR）. Metal NPs prepared by laser ablation in liquid method and the effect of laser parameters on the size, distribution, wavelength of SPR of Ag, Au, and mixture of Ag-Au, and Ag core/Au shell NPs are investigated. Our results show that the adjustable SPR band can be achieved in each class of NPs which is suitable for adjustable optical window applications.     

荧光/表面增强拉曼散射双模式纳米光学探针的构建及性能研究

提出一种新型的荧光及表面增强拉曼散射（SERS）双模式光学纳米探针。首先,通过再沉淀-包覆法合成二氧化硅包覆香豆素6的纳米颗粒,再在二氧化硅表面静电吸附多聚赖氨酸分子形成包覆层,随后通过原位还原的方法在多聚赖氨酸壳层复合银纳米颗粒,最后在银纳米颗粒表面吸附拉曼分子即形成双模式纳米探针。该探针通过二氧化硅包覆的荧光分子产生荧光信号,以多聚赖氨酸表面的银纳米颗粒作为SERS增强基底,利用拉曼分子获得SERS信号,实现了荧光及SERS双模式成像。荧光与表面增强拉曼散射相结合的双模式分析技术可同时发挥二者的优点,提高成像的分辨率和灵敏度,在生物医学领域具有重要的应用价值。     

Janus Particles: Metallic Janus and Patchy Particles (Part. Part. Syst. Charact. 1/2013)

The concepts of Janus and patchy particles are relatively new in nanoscience. Much effort has been made during recent years to devise and fabricate asymmetric particles with multiple compositions and functionalities due to their interesting properties and potential applications in a variety of fields such as catalysis, optical imaging, or drug delivery. Here, recent advances in the field of Janus particles are highlighted, focusing on nanoparticles comprising (at least) one metallic component, which is responsible for the most interesting properties of the particles. First, the main synthetic approaches are summarized, i.e., phase separation, masking, and self‐assembly techniques, and then the special properties, applications, and future prospects of metallic Janus particles are described.     

Influence of size and surface capping on photoluminescence and cytotoxicity of gold nanoparticles

Hydrophilic and homogeneous sub-10 nm blue light-emitting gold nanoparticles (NPs) functionalized with different capping agents have been prepared by simple chemical routes. Structure, average, size, and surface characteristics of these NPs have been widely studied, and the stability of colloidal NP solutions at different pH values has been evaluated. Au NPs show blue PL emission, particularly in the GSH capped NPs, in which the thiol-metal core transference transitions considerably enhance the fluorescent emission. The influence of capping agent and NP size on cytotoxicity and on the fluorescent emission are analyzed and discussed in order to obtain Au NPs with suitable features for biomedical applications. Cytotoxicity of different types of gold NPs has been determined using NPs at high concentrations in both tumor cell lines and primary cells. All NPs used show high biocompatibility with low cytotoxicity even at high concentration, while Au-GSH NPs decrease viability and proliferation of both a tumor cell line and primary lymphocytes.     

Copolymer Particles with Incorporated Gold and Silver Nanoparticles to Absorb Short‐Wavelength Scattering in Full‐Color Photonic Glasses

Photonic glasses (PGs) have fascinated researchers because the structural colors that are reflected from PGs are angle independent. However, low color saturation, especially for colors at longer wavelengths, is an obstacle for realizing full‐color PGs. It is reported that the form‐factor‐(FF)‐derived reflections that degrade the color saturation of PGs can be removed by embedding Ag and Au nanoparticles (NPs) into copolymers. Styrene and 4‐vinylpyridne copolymer particles are prepared and used as nanotemplates to synthesize AgNPs and AuNPs. The wavelength of the FF‐derived reflections in relation to the diameter of the particles is estimated. NPs with an absorption spectrum corresponding to the calculated values are then selectively embedded in the copolymer particles. PGs fabricated with AgNP‐ and AuNP‐embedded copolymer particles exhibit fewer FF‐derived reflections owing to the surface‐plasmon‐resonance‐induced absorption of the embedded NPs. Using these FF‐reduced PGs, angle‐independent full‐color PG pigments are realized.     

HoF3 and DyF3 Nanoparticles as Contrast Agents for High‐Field Magnetic Resonance Imaging

Clinical contrast agents (CAs) currently used in magnetic resonance imaging (MRI) at low fields are less effective at high magnetic fields. The development of new CAs is mandatory to improve diagnostic capabilities of the new generation of high field MRI scanners. The purpose of this study is to synthesize uniform, water dispersible LnF₃ (Ln = Ho, Dy) nanoparticles (NPs) and to evaluate their relaxivity at high magnetic field (9.4 T) as a function of size and composition. Two different types of HoF₃ NPs are obtained by homogeneous precipitation in ethylene glycol at 120 °C. The use of holmium acetate as holmium precursor leads to rhombus‐like nanoparticles, while smaller, ellipsoid‐like nanoparticles are obtained when nitrate is used as the holmium salt. To explain this behavior, the mechanism of formation of both kinds of particles is analyzed in detail. Likewise, rhombus‐like DyF₃ nanoparticles are prepared following the same method as for the rhombus‐like HoF₃ nanoparticles. We have found, to the best of knowledge, the highest transverse relaxivity values at 9.4 T described in the literature for this kind of CAs. Finally, the LnF₃ NPs have shown negligible cytotoxicity for C6 rat glioma cells for concentrations up to 0.1 mg mL^?1.     

电场辅助溶解法实现玻璃表面金纳米粒子的形貌控制

贵金属纳米粒子由于其非常独特的光学特性和表面活性, 在光子学、 催化和生物标识等方面都有非常重要的应用. 采用离子溅射和后续热处理相结合的方法在玻璃表面形成了尺寸大约为60-80 nm的单分散的球形金纳米粒子. 在适当的温度条件下, 采用步进式增加的强直流电场, 实现了金纳米粒子的电场辅助溶解过程. 在玻璃表面的不同颜色区域, 初始球形的金纳米粒子溶解成月蚀状形貌. 结合不同颜色区域内金纳米粒子的表面等离子体共振吸收性质和扫描电镜照片, 研究了实验条件对金纳米粒子性质的影响. 结合电场辅助溶解实验过程中的电流-电压特性, 分析了金纳米粒子在强直流电场辅助下溶解的物理过程: 金粒子中动出的电子向阳极的隧穿过程作为开始, 随后是金阳离子向玻璃基体中的传输过程和阴极提供的电子与带有正电荷的金粒子相结合的过程. 详细讨论了电场辅助溶解法实现金纳米粒子形貌控制的物理机制.     

Simple method to prepare size‐controllable gold nanoparticles in solutions and their applications on surface‐enhanced Raman scattering

We report here, for the first time, a simple method to prepare size‐controllable Au nanoparticles (NPs) in aqueous solutions from bulk Au substrates. First, chitosan (Ch)‐capped Au‐containing complexes were prepared by electrochemical oxidation–reduction cycles in 0.1 N NaCl and 1 g/l Ch solutions. Then the solutions were heated from room temperature to boiling at different heating rates to synthesize size‐controllable Au NPs. The particle sizes of the prepared Au(111) NPs could be controlled from 5 to 30 nm with an increase of the heating rate during preparation. Experimental results indicate that the prepared Au(111) NPs with diameters ranging from 10 to 30 nm can serve as surface‐enhanced Raman scattering active probes for molecules of rhodamine 6G. Copyright © 2010 John Wiley & Sons, Ltd.     

Size-controlled synthesis of superparamagnetic iron oxide nanoparticles and their surface coating by gold for biomedical applications

The size mono-dispersity, saturation magnetization, and surface chemistry of magnetic nanoparticles (NPs) are recognized as critical factors for efficient biomedical applications. Here, we performed modified water-in-oil inverse nano-emulsion procedure for preparation of stable colloidal superparamagnetic iron oxide NPs (SPIONs) with high saturation magnetization. To achieve mono-dispersed SPIONs, optimization process was probed on several important factors including molar ratio of iron salts [Fe³⁺ and Fe²⁺], the concentration of ammonium hydroxide as reducing agent, and molar ratio of water to surfactant. The biocompatibility of the obtained NPs, at various concentrations, was evaluated via MTT (3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide) assay and the results showed that the NPs were non-toxic at concentrations <0.1 mg/mL. Surface functionalization was performed by conformal coating of the NPs with a thin shell of gold (∼4 nm) through chemical reduction of attached gold salts at the surface of the SPIONs. The Fe₃O₄ core/Au shell particles demonstrate strong plasmon resonance absorption and can be separated from solution using an external magnetic field. Experimental data from both physical and chemical determinations of the changes in particle size, surface plasmon resonance optical band, phase components, core–shell surface composition, and magnetic properties have confirmed the formation of the mono-dispersed core–shell nanostructure.     

Surface‐enhanced Raman scattering spectroscopy via gold nanostars

Anisotropic metallic nanoparticles (NPs) have unique optical properties, which lend them to applications such as surface‐enhanced Raman scattering (SERS) spectroscopy. Star‐shaped gold (Au) NPs were prepared in aqueous solutions by the seed‐mediated growth method and tested for Raman enhancement using 2‐mercaptopyridine (2‐MPy) and crystal violet (CV) probing molecules. For both molecules, the SERS activity of the nanostars was notably stronger than that of the spherical Au NPs of similar size. The Raman enhancement factors (EFs) for 2‐MPy on Au nanostars and nanorods are comparable and estimated as greater than 5 orders of magnitude. However, the enhancement for CV on nanostars was significantly higher than for nanorods, in particular at CV concentrations of 100 nM or lower. This article is a US Government work and is in the public domain in the USA. Published in 2008 by John Wiley & Sons, Ltd.     

Designing Zwitterionic SiO2NH2‐Au Particles with Tunable Patchiness using Wrinkles

A facile template‐based approach toward zwitterionic SiO₂NH₂‐Au patchy particles is presented. Therefore, wrinkle templates prepared by stress release in a bilayer system comprised of an elastic PDMS fundament and a thin SiO_x top layer are used. After aligning positively charged, amine‐functionalized silica particles in wrinkle grooves, their surfaces are partially modified with negatively charged gold nanoparticles in an electrostatic adsorption step. Patchiness is precisely controlled by the degree of immersion of the initial particles into wrinkles of varying dimensions. By ultrasonication or wetting with a water droplet, patchy particles are easily released from the substrate‐yielding particles with two oppositely charged hemispheres. Interfacial tension measurements prove the surface activity of the SiO₂NH₂‐Au particles in an oil/water system and are explained in the view of the Janus‐type surface charges of the particles and the charge of the oil/water interface.