Fabrication of conducting polymer micro/nanostructures coated with Au nanoparticles for electrochemical sensors

Polypyrrole (PPy) micro/nanostructures coated with Au nanoparticles were prepared by electropolymerization and electro-deposition. Two types of PPy structures, micro-embossed and nanowire forest, were synthesized on patterned gold electrodes using different aqueous solutions, and Au nanoparticles were coated onto the PPy micro/nanostructure surface. The size of the Au nanoparticles ranged from 10 to 100 nm, and the maximum density of the nanoparticles was 73 particles/microm2. The small size and high density of the Au nanoparticles were achieved by optimizing the deposition time and chloroauric acid (HAuCl4) concentration. Cyclic voltammograms of ferrocyanide oxidation showed that the PPy micro/nanostructures coated with Au nanoparticles exhibit good electrochemical activity. These high-performance electrodes can be used in electrochemical sensors because the Au nanoparticles enhance electron transfer and provide a binding site for biomarker molecules, such as DNA, protein, and aptamers.     

Controlled synthesis of 2D Au nanostructure assembly with the assistance of sulfonated polyaniline nanotubes

A wet chemical approach is used successfully to produce nanostructured Au material by the reduction of sulfonated polyaniline (SPANI) nanotubes. The Au nanostructures obtained are composed of single crystal Au nanoplates, which are aggregated layer-by-layer into stacks or edge-on-face into clusters at various conditions. The Au nanoplate diameter and thickness can be conveniently controlled in the range of 100?nm to 2?μm and 10 to 30?nm, respectively, with no accompanying single Au nanoparticles being observed. The formation of the Au nanostructures was controlled by the degradation of SPANI. The gradually and slowly released segments of SPANI served as the reductant during the growth of the 2D Au nanostructures.     

Synthesis of silica/Au core-shell nanostructures by galvanic replacement of silica/Ag in aqueous and alkaline medium

We present here a facile one-step method for the synthesis of silica/Au core-shell nanostructures by exploiting the potential difference of AuCl₄^? and Ag in aqueous as well as alkaline media. Initially, silica/Ag core-shell nanostructures were synthesised by coating Ag nanoparticles on silica core (size ～150 nm) in a two-step process (seeding and growth) and were characterised for their morphological, structural and optical behaviours. A complete coverage of silica core with Ag nanoparticles was seen from scanning electron microscope and transmission electron microscope images. The presence of resonance peaks in the optical spectrum manifests the nature of the shell (thin shell ～413 and 650 nm, thick shell ～434 nm). Galvanic replacement of silica/Ag core-shell nanostructures in chloroauric acid solution (HAuCl₄) was studied in both the aqueous and alkaline medium, where an aqueous environment results into fast and effective replacement as compared to an alkaline medium, which has been confirmed from optical absorption studies. The optical studies showed that in an alkaline environment, on galvanic replacement of Ag with Au, the individual absorption peak of Ag (～414 nm) and Au (～520 nm) disappeared, whereas new absorption wavelengths in higher region (600–800 nm) of electromagnetic spectrum were observed. A detailed mechanism is proposed for the same to explain this behaviour. A range of novel new plasmonic core-shell nanomaterials can be synthesised as an intermediate of this facile one-step reaction.     

Tailoring the photoluminescence of ZnO nanowires using Au nanoparticles

Rational design of hybrid nanostructures through attaching nanowires with nanoparticles is an effective route to enhance the existing functionalities or to explore new ones. We carry out a systematic investigation on the photoluminescence of ZnO nanowire-Au nanoparticle hybrid nanostructures synthesized by attaching Au nanoparticles onto ZnO nanowires. Citrate-stabilized 40?nm Au nanoparticles effectively quench the green emission and enhance the UV emission of the ZnO nanowires, which is consistent with the wavelength-dependent generation of surface plasmon. The UV/green emission intensity ratio could be reversibly and reproducibly tailored by attaching/detaching Au nanoparticles. This enhancement of UV emission diminishes if the Au nanoparticles are coated with a polymer layer. We also find that the orange-red emission of the ZnO nanowires is related to the excess oxygen on the ZnO surface, and it is also tunable via annealing and surface modifications.     

Electrochemical deposition of polypyrrole nanolayers on discontinuous ultrathin gold films

Ultrathin layers of polypyrrole (PPy) were electrochemically grown between microelectrodes on a Si/SiO(2) substrate. Conducting nanolayers of PPy are directly grown onto ultrathin discontinuous gold (Au) film between the microelectrodes, with thicknesses in the range 10-100?nm. The system therefore forms a novel (PPy/Au) nanocomposite conductor. Atomic force microscopy (AFM) imaging and conductivity measurements indicate that at all thicknesses a relatively uniform film is formed but with significant roughness that reflects the roughness of the metallic island layer. In PPy/Au films with thickness ～10?nm, the small barriers around the gold islands dominate the conduction, and as the film thickness increases to 100?nm the intrinsic conductivity of highly doped PPy dominates the charge transport.     

以酯端基PAMAM树形分子为模板在N，M-二甲基甲酰胺溶剂中制备金纳米粒子

用UV-vis、FT-IR光谱研究了HAuCl4和酯端基聚酰胺胺(PAMAM)树形分子在N，N-二甲基甲酰胺(DMF)溶剂中的相互作用，提出HAuCl4与树形分子之间的络合机理：[AuCl4]^-离子与质子化叔胺基团形成离子对，Au^3 离子与PAMAM树形分子上的酯基和酰胺基团形成配位作用。在DMF溶剂中酯端基PAMAM树形分子与HAuCl4配位后用柠檬酸钠还原形成金纳米粒子，UV-vis光谱和TEM图像分析表明了随树形分子代数的增加，金纳米粒子的直径减小，并提出了树形分子-金纳米复合物的结构模型：(1)较低代数的树形分子环绕在金粒子的外围；(2)在较高代数的树形分子空腔内部封装金纳米粒子。     

Observation on growth process of gold Y- and phi-shaped nanoparticles in solutions

The morphological evolution of gold (Au) nanoparticles is demonstrated via TEM and UV-vis spectroscopy in a real-time basis. Y-shaped and phi-shaped Au nanoparticles were prepared by a seed mediated method at 0 degrees C. The evolution of shape ranging from spheres to Y- and phi-shapes was characterized by UV-vis spectroscopy. For the spherical particles, the corresponding transverse plasmon absorption (540 nm) was observed at the initial growth stage. As further growth proceeded, new peaks appeared at ca. 620 nm and ca. 700-1000 nm, which was to the characteristic peak of Y-shaped and phi-shaped nanoparticles, respectively. In addition, all intermediate steps were observed in the morphology change by TEM. At the initial step, spherical particles with 20 nm size were generated and the particles were gradually evolved from tiny triangular shape or I-shape to Y- and phi-shape. In this study, the growth mechanism of Au nanoparticles was investigated by the characterization of optical properties as well as morphologies with respect to reaction time.     

Interface controlled growth of nanostructures in discontinuous Ag and Au thin films fabricated by ion beam sputter deposition for plasmonic applications

The growth of discontinuous thin films of Ag and Au by low energy ion beam sputter deposition is reported. The study focuses on the role of the film?Csubstrate in determining the shape and size of nanostructures achieved in such films. Ag films were deposited using Ar ion energy of 150?eV while the Au films were deposited with Ar ion energies of 250?C450?eV. Three types of interfaces were investigated in this study. The first set of film?Csubstrate interfaces consisted of Ag and Au films grown on borosilicate glass and carbon coated Cu grids used as substrates. The second set of films was metallic bilayers in which one of the metals (Ag or Au) was grown on a continuous film of the other metal (Au or Ag). The third set of interfaces comprised of discontinuous Ag and Au films deposited on different dielectrics such as SiO₂, TiO₂ and ZrO₂. In each case, a rich variety of nanostructures including self organized arrays of nanoparticles, nanoclusters and nanoneedles have been achieved. The role of the film?Csubstrate interface is discussed within the framework of existing theories of thin film nucleation and growth. Interfacial nanostructuring of thin films is demonstrated to be a viable technique to realize a variety of nanostructures. The use of interfacial nanostructuring for plasmonic applications is demonstrated. It is shown that the surface Plasmon resonance of the metal nanostructures can be tuned over a wide range of wavelengths from 400 to 700?nm by controlling the film?Csubstrate interface.     

Enhancement of field emission and photoluminescence properties of graphene-SnO2 composite nanostructures

In this study, the SnO(2) nanostructures and graphene-SnO(2) (G-SnO(2)) composite nanostructures were prepared on n-Si (100) substrates by electrophoretic deposition and magnetron sputtering techniques. The field emission of SnO(2) nanostructures is improved largely by depositing graphene buffer layer, and the field emission of G-SnO(2) composite nanostructures can also further be improved by decreasing sputtering time of Sn nanoparticles to 5 min. The photoluminescence (PL) spectra of the SnO(2) nanostructures revealed multipeaks, which are consistent with previous reports except for a new peak at 422 nm. Intensity of six emission peaks increased after depositing graphene buffer layer. Our results indicated that graphene can also be used as buffer layer acting as interface modification to simultaneity improve the field emission and PL properties of SnO(2) nanostructures effectively.     

Light guide of Au nanostructures for color-filterness optoelectronic display devices

Au line nanostructures with different pitch distances from 500 nm to 950 nm on ITO coated glass substrates have been fabricated at room temperature for exploring the color light guide in all kinds of display system. The patterned Au line array is used as a light outcoupling and color-selection component due to the emission wavelength changed by the Au line arrays with different pitch distances that could achieve multi-color selections. The ITO coated glass substrates patterned with periodic Au line arrays with controlled line pitches has been demonstrated and used as a color filter in all display devices. Using a proper pitch distance of Au line nanostructures, the basic third colors of red, green, and blue (RGB) can be simply gained and controlled without a traditional color filter for future optoelectronic display devices.     

Synthesis of dendrimer-stabilized gold-polypyrrole core-shell nanoparticles

Core-shell composite nanoparticles consisting of a gold core and polypyrrole shell were prepared and stabilized with the poly(amidoamine) dendrimer. An in situ redox polymerization technique was used in which pyrrole reduced Au3+ to Au and then oxidized to polypyrrole. The presence of gold nanoparticles as a core was characterized by its surface plasmon absorption peak at 534 nm. Fourier transform infrared spectroscopy confirmed the presence of polypyrrole on the nanoparticle surfaces. The average diameter of the core-shell nanoparticle is 8.7 +/- 1.8 nm with a shell thickness of approximately 1.5-2.0 nm as estimated from the transmission electron microscopy image. Dissolution of the Au core using KCN enabled the formation of hollow polymer nanospheres.     

Sensitive human interleukin 5 impedimetric sensor based on polypyrrole-pyrrolepropylic acid-gold nanocomposite

A sensitive impedimetric immunosensor was constructed by using an electropolymerized nanocomposite film containing polypyrrole (PPy), polypyrrolepropylic acid (PPa), and Au nanoparticles. The nanocomposite exhibits good stability, high porosity, high hydrophilicity, and efficient probe immobilization capability. In the film, PPa enhances the hydrophilicity while providing covalent probe attachment linkers, PPy promotes the conductivity and electroactivity, and Au nanoparticles result in good conductivity, high stability, and covalent binding linkers. These combined advantages significantly improve the detection sensitivity in comparison to the conventional methods. As a model, a human interleukin 5 (IL-5) immunosensor, an important sensor for disease pathology study, clinic diagnosis, and pharmaceutical research, was fabricated with the new nanocomposite film. Various optimization works were conducted to improve the detection sensitivity. With the optimal fabrication parameters, the detection limit for IL-5 was 10 fg/mL in phosphate buffered saline (PBS) and 1 pg/mL in 1% human serum with good specificity and a dynamic range of 3 orders of magnitude. This work demonstrates a new approach to develop a sensitive and labeless impedimetric immunosensor for potential broad applications in clinical diagnosis and drug discovery.     

Intrinsically Fluorescent,Stealth Polypyrazoline Nanoparticles with Large Stokes Shift for In Vivo Imaging

Recent advances in super‐resolution microscopy and fluorescence bioimaging allow exploring previously inaccessible biological processes. To this end, there is a need for novel fluorescent probes with specific features in size, photophysical properties, colloidal and optical stabilities, as well as biocompatibility and ability to evade the reticuloendothelial system. Herein, novel fluorescent nanoparticles are introduced based on an inherently fluorescent polypyrazoline (PPy) core and a polyethylene glycol (PEG) shell, which address all aforementioned challenges. Synthesis of the PPy‐PEG amphiphilic block copolymer by phototriggered step‐growth polymerization is investigated by NMR spectroscopy, size‐exclusion chromatography, and mass spectrometry. The corresponding nanoparticles are characterized for their luminescent properties and hydrodynamic size in various aqueous environments (e.g., cell culture media). PPy nanoparticles particularly exhibit a large Stokes shift (Δλ = 160 nm or Δν > 7000 cm^?1) with visible light excitation and strong colloidal stability. While clearance by macrophages and endothelial cells is minimal, PPy displays good biocompatibility. Finally, PPy nanoparticles prove to be long circulating when injected in zebrafish embryos, as observed by in vivo time‐lapse fluorescence microscopy. In summary, PPy nanoparticles are highly promising to be further developed as fluorescent nanodelivery systems with low toxicity and exquisite retention in the blood stream.     

Synthesis of porous ZnO nanostructures using bamboo fibers as templates

In this study, we fabricated ZnO nanostructures using bamboo fibers as templates. The starting material used was zinc acetate, and the nanostructures were synthesized by soaking and calcining the bamboo fibers. The fabricated nanostructures were characterized using X-ray powder diffraction (XRD) analysis, scanning electron microscopy (SEM), and ultraviolet-visible spectrophotometry. The results showed that the size of the ZnO nanoparticles was approximately 20–100 nm. When the ZnO nanoparticles were used as the catalyst in the photodegradation of methyl orange, the dye degraded by 95.98 % in 80 min. The response and recovery times of a gas sensor based on the ZnO nanoparticles were 25 and 24 s, respectively, during the detection of C₂H₅OH in a concentration of 10 ppm at 270 °C.     

Synthesis and characterization of novel Ag-polypyrrole@poly(styrene-co-methacrylic acid) nanocomposite particles

Novel raspberry-like Ag-polypyrrole/poly(styrene-co-methacrylic acid) (Ag-PPy/P(St-co-MAA)) colloidal nanocomposite particles were prepared by aqueous oxidative polymerization of pyrrole using AgNO₃ as the oxidant. The polymerization was carried out in the pre-synthesized polymer-emulsion of P(St-co-MAA) with emulsifier-free P(St-co-MAA) latex particles serving as both the templates and the stabilizers. Without any extra surfactants or polymer stabilizers, the polymerization proceeded steadily with the in-situ produced Ag-PPy nanocomposites depositing on the surface of the template particles. The obtained product is typical of raspberry-like morphology, whose nanostructures and compositions were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), powder X-ray diffraction (XRD) and electron dispersive X-ray spectrometer (EDS), respectively. The results confirmed that the surface of the P(St-co-MAA) latex was coated by Ag-PPy nanocomposite particles with a size range from 2 nm to 50 nm. Most of Ag nanoparticles are encapsulated by the PPy sheath or dispersed in the PPy layer.     

Au–ZnO hybrid nanostructures prepared by electro-exploding wire technique: Raman signal enhancement and photoluminescence emission quenching

Electro-exploding wire (EEW) technique was employed to prepare ZnO and Au–ZnO hybrid nanoparticles. Average size of the prepared ZnO nanoparticles is found to be 3.8 nm and uniform throughout. These ultrafine ZnO nanoparticles are found to agglomerate around the highly surface active Au nanoparticles. It also acts as a stabilizer for the Au nanoparticles by avoiding self agglomeration. The hybrid nanocrystals show strong crystallinity of face-centered cubic and hexagonal wurtzite structure of gold (Au) and zinc oxide (ZnO), respectively. Presence of Au₃Zn in pristine sample is a clear indication of a strong interaction between ZnO and Au systems. The hybrid system shows strong enhancement in the ZnO Raman signals and quenching in the visible Photoluminescence (PL) emission. Energy-dependent PL analysis shows the dominance of the surface defects over the bulk contribution in these ultrafine ZnO and Au–ZnO hybrid nanostructures.     

Quantitative characterization of gold nanoparticles by field-flow fractionation coupled online with light scattering detection and inductively coupled plasma mass spectrometry

An analytical platform coupling asymmetric flow field-flow fractionation (AF(4)) with multiangle light scattering (MALS), dynamic light scattering (DLS), and inductively coupled plasma mass spectrometry (ICPMS) was established and used for separation and quantitative determination of size and mass concentration of nanoparticles (NPs) in aqueous suspension. Mixtures of three polystyrene (PS) NPs between 20 and 100 nm in diameter and mixtures of three gold (Au) NPs between 10 and 60 nm in diameter were separated by AF(4). The geometric diameters of the separated PS NPs and the hydrodynamic diameters of the Au and PS NPs were determined online by MALS and DLS, respectively. The three separated Au NPs were quantified by ICPMS and recovered at 50-95% of the injected masses, which ranged between approximately 8-80 ng of each nanoparticle size. Au NPs adhering to the membrane in the separation channel was found to be a major cause for incomplete recoveries. The lower limit of detection (LOD) ranged between 0.02 ng Au and 0.4 ng Au, with increasing LOD by increasing nanoparticle diameter. The analytical platform was applied to characterization of Au NPs in livers of rats, which were dosed with 10 nm, 60 nm, or a mixture of 10 and 60 nm nanoparticles by intravenous injection. The homogenized livers were solubilized in tetramethylammonium hydroxide (TMAH), and the recovery of Au NPs from the livers amounted to 86-123% of their total Au content. In spite of successful stabilization with bovine serum albumin even in alkaline medium, separation of the Au NPs by AF(4) was not possible due to association with undissolved remains of the alkali-treated liver tissues as demonstrated by electron microscopy images.     

Facile Synthesis of Anisotropic Au Nanostructures by Laser Irradiation and Study of Their Optical and Electrokinetic Properties

This work describes a cost-effective single step technique for the preparation of Au nanostructures of many anisotropic shapes from Au nanorods by irradiating them with different laser energies (2.71, 2.54, and 2.41 eV). A variety of many irregular Au nanomorphologies such as multifaceted polygonal spheres (10–20 nm), low aspect ratio rods, oval egg shapes, squares, pentagons, and nanocapsules of varying sizes were formed after laser exposure. The small irregular shaped particles with new surface exposed atoms having cutting edges and sharp corners affect the optical, electrokinetic, and catalytic properties of fragmented Au nanoparticles. The percentage decomposition of Au nanorods is found to increase as 59% > 69% > 72% with increased energy of laser exposure; 2.41 eV (514.7 nm) > 2.50 eV (488 nm) > 2.71 eV (457.9 nm), as determined from the TEM images. The formation of quantum sized paticles upon laser irradiation results in the increase of zeta potential from +50.0 to +57.5 mV and conductance values. The co-catalytic activity of photofragmented Au nanorods is ～20–25% higher than that of bare nanorods for benzaldehyde photooxidation.     

Synthesis, morphology and optical properties of multi-pods Au/FeO(OH) and Au/Fe2O3 nanostructures

Multi-pods Au/FeOOH nanostructures were synthesized by a hydrothermal treatment of an aqueous solution of mixed micellar formed by gold nanoparticles, hexadecyltrimethyl ammonium bromide (CTAB), and (NH₄)₃[FeF₆] at 160 °C for 48 h and sequential calcined at 290 °C for 1.5 h, resulting in the formation of multi-pods Au/Fe₂O₃ nanostructures. The as-obtained products were characterized by powder X-ray diffraction, transmission electron microscopy, selected area electron diffraction, field emission scanning electron microscopy, and UV-vis spectroscopy. Surface plasmon resonance band of gold nanoparticles was observed in the multi-pods Au/FeOOH nanostructures. However, a similar behavior was not seen with multi-pods Au/Fe₂O₃ nanostructures. The critical role of F⁻ ions and CTAB molecules in the formation of FeO(OH) multipods and the probable mechanism of the formation of multi-pods Au/FeOOH and Au/Fe₂O₃ nanostructures were discussed.     

Surface-enhanced Raman scattering inside Au@Ag core/shell nanorods

The design and synthesis of plasmonic nanoparticles with Raman-active molecules embedded inside them are of significant interest for sensing and imaging applications.However,direct synthesis of such nanostructures with controllable shape,size,and plasmonic properties remains extremely challenging.Here we report on the preparation of uniform Au@Ag core/shell nanorods with controllable Ag shells of 1 to 25 nm in thickness.1,4-Aminothiophenol (4-ATP) molecules,used as the Raman reporters,were located between the Au core and the Ag shell.Successful embedding of reporter molecules inside the core/shell nanoparticles was confirmed by the absence of selective oxidation of the amino groups,as measured by Raman spectroscopy.The dependence of Raman intensity on the location of the reporter molecules in the inside and outside of the nanorods was studied.The molecules in the interior showed strong and uniform Raman intensity,at least an order of magnitude higher than that of the molecules on the nanoparticle surface.In contrast to the usual surface-functionalized Raman tags,aggregation and clustering of nanoparticles with embedded molecules decreased the surface-enhanced Raman scattering (SERS) signal.The findings from this study provide the basis for a novel detection technique of low analyte concentration utilizing the high SERS response of molecules inside the core/shell metal nanostructures.As an example,we show robust SERS detection of thiram fungicide as low as 10-9 M in solutions.