Ultrafast growth of dendritic gold nanostructures and their applications in methanol electro-oxidation and surface-enhanced Raman scattering

A simple and rapid solution-phase synthesis of dendritic gold nanostructures with hyperbranched architecture is demonstrated in this report. Further investigations revealed that the morphology of the synthesized sample depended on proper parameters such as reagent concentration, reaction temperature, reagent addition sequence and stir. Moreover, the dendritic gold nanostructures exhibited a good electrocatalytic activity toward methanol electro-oxidation. When compared with sea-urchinlike and flowerlike gold nanostructures which were prepared by varying the parameters of experiment, dendritic gold nanostructures showed the highest surface-enhanced Raman scattering (SERS) sensitivity using 4-aminothiophenol (4-ATP) as probe molecules. The dendritic gold nanostructures may find potential applications in catalysis, SERS and biosensor.     

Surfactantless photochemical deposition of gold nanoparticles on an optical fiber core for surface-enhanced Raman scattering

Surface-enhanced Raman scattering (SERS) probes based on gold nanoparticles modifying the core of the optical fiber were made by a surfactantless photochemical deposition method. The growth kinetics and shape evolution of gold nanoparticles depending on different experimental conditions were studied. It was found that, under the condition of detectable gold nanoparticle deposition, increasing the concentration of chloroauric acid (HAuCl(4)) was not conducive to the deposition whereas increasing the concentration of sodium citrate (Na(3)Ct) would speed up the deposition. By controlling the concentration of the reaction solution and irradiation time, we obtained fused spherical-like, spherical, and flowerlike gold nanoparticles. To test the SERS activity of the probes, the SERS spectra of a rhodamine 6G aqueous solution were recorded in direct detection mode and remote mode. We have also developed a new approach to improving the SERS sensitivity when detecting in remote mode.     

Silica-void-gold nanoparticles: temporally stable surface-enhanced Raman scattering substrates

Reproducible detection of a target molecule is demonstrated using temporally stable solution-phase silica-void-gold nanoparticles and surface-enhanced Raman scattering (SERS). These composite nanostructures are homogeneous (diameter = 45 +/- 4 nm) and entrap single 13 nm gold nanoparticle cores inside porous silica membranes which prevent electromagnetic coupling and aggregation between adjacent nanoparticles. The optical properties of the gold nanoparticle cores and structural changes of the composite nanostructures are characterized using extinction spectroscopy and transmission electron microscopy, respectively, and both techniques are used to monitor the formation of the silica membrane. The resulting nanostructures exhibit temporally stable optical properties in the presence of salt and 2-naphthalenethiol. Similar SERS spectral features are observed when 2-naphthalenethiol is incubated with both bare and membrane-encapsulated gold nanoparticles. Disappearance of the S-H Raman vibrational band centered at 2566 cm(-1) with the composite nanoparticles indicates that the target molecule is binding directly to the metal surface. Furthermore, these nanostructures exhibit reproducible SERS signals for at least a 2 h period. This first demonstration of utilizing solution-phase silica-void-gold nanoparticles as reproducible SERS substrates will allow for future fundamental studies in understanding the mechanisms of SERS using solution-phase nanostructures as well as for applications that involve the direct and reproducible detection of biological and environmental molecules.     

Bimetallic gold–silver nanoplate array as a highly active SERS substrate for detection of streptavidin/biotin assemblies

The silver-modified gold nanoplate arrays as bimetallic surface-enhanced Raman scattering (SERS) substrates were optimized for the surface-enhanced Raman detection of streptavidin/biotin monolayer assemblies. The bimetallic gold–silver nanoplate arrays were fabricated by coating silver nanoparticles uniformly on the gold nanoplate arrays. Depending on silver nanoparticle coating, the localized surface plasmon resonance (LSPR) peak of the bimetallic gold–silver nanoplate arrays blue-shifted and broadened significantly. The common probe molecule, Niel Blue A sulfate (NBA) was used for testing the SERS activity of the bimetallic gold–silver nanoplate arrays. The SERS intensity increased with the silver nanoparticle coating, due to a large number of hot spots and nanoparticle interfaces. The platforms were tested against a monolayer of streptavidin functionalized over the bimetallic gold–silver nanoplate arrays showing that good quality spectra could be acquired with a short acquisition time. The supramolecular interaction between streptavidin (strep) and biotin showed subsequent modification of Raman spectra that implied a change of the secondary structure of the host biomolecule. And the detection concentration for biotin by this method was as low as 1.0 nM. The enhanced SERS performance of such bimetallic gold–silver nanoplate arrays could spur further interest in the integration of highly sensitive biosensors for rapid, nondestructive, and quantitative bioanalysis, particularly in microfluidics.     

Chemically bound gold nanoparticle arrays on silicon: assembly, properties and SERS study of protein interactions

A highly reproducible and facile method for formation of ordered 2 dimensional arrays of CTAB protected 50 nm gold nanoparticles bonded to silicon wafers is described. The silicon wafers have been chemically modified with long-chain silanes terminated with thiol that penetrate the CTAB bilayer and chemically bind to the underlying gold nanoparticle. The silicon wafer provides a reproducibly smooth, chemically functionalizable and non-fluorescent substrate with a silicon phonon mode which may provide a convenient internal frequency and intensity calibration for vibrational spectroscopy. The CTAB bilayer provides a potentially biomimetic environment for analyte, yet allows a sufficiently small nanoparticle separation to achieve a significant electric field enhancement. The arrays have been characterized using SEM and Raman spectroscopy. These studies reveal that the reproducibility of the arrays is excellent both between batches (<10% RSD) and across a single batch (<5% RSD). The arrays also exhibit good stability, and the effect of temperature on the arrays was also investigated. The interaction of protein and amino acid with the nanoparticle arrays was investigated using Raman microscopy to investigate their potential in bio-SERS spectroscopy. Raman of phenylalanine and the protein bovine pancreatic trypsin inhibitor, BPTI were studied using 785 nm excitation, coincident with the surface plasmon absorbance of the array. The arrays exhibit SERS enhancements of the order of 2.6 x 10(4) for phenylalanine, the standard deviation on the relative intensity of the 1555 cm(-1) mode of phenylalanine is less than 10% for 100 randomly distributed locations across a single substrate and less than 20% between different substrates. Significantly, comparisons of the Raman spectra of the protein and phenylalanine in solution and immobilized on the nanoparticle arrays indicates that the protein is non-randomly orientated on the arrays. Selective SERS enhancements suggest that aromatic residues penetrate through the bilayer inducing conformational changes in the protein.     

Fabrication of Au hybrid protein chips and its application to SERS-based bioassay

Hybrid micro/nanostructures composed with alternative Au nanoparticle (NP) arrays and protein dots were fabricated via layer-by-layer self-assembly and the microsphere lithography technique. These micro/nanostructures were novel protein chips which had applications in the surface-enhanced Raman spectroscopy (SERS) based immunoassay. The synthetic processes were to fabricate Au nanowell arrays initially by using the templates of ordered monolayers of polystyrene (PS) microsphere arrays. Then, the proteins of antibody (avidin) were imbedded in the Au nanowells. Lastly, the immune reaction was implemented by adding atto 610-biotin. SERS spectra were recorded as the immunoassay readout, which showed the lowest detective concentration of 100 pg/mL. These new kind of SERS-based protein chips were easy to fabricate, inexpensive and supersensitive, and exhibit the potential application in bioassays, forensics and biosensors.     

Electrochemical synthesis of gold nanocrystals and their 1D and 2D organization

Size-controlled gold nanocrystals were conveniently synthesized through direct electroreduction of bulk AuCl(4)(-) ions in the presence of poly(N-vinylpyrrolidone) (PVP). PVP greatly enhanced the gold particle formation process and also significantly retarded the gold electrodeposition process, allowing the electrochemical synthesis of gold nanocrystals to be carried out in the form of simple electroreduction. This novel electrochemical method may be extended to synthesis of other noble metal nanoparticles with controllable size on a large scale. The PVPK90-protected gold nanocrystals spontaneously self-assembled into nearly ordered 2D close-packed arrays and interesting 1D nanostructures. The aggregation of unstable PVPK17-protected gold nanocrystals resulted in the formation of ultrathin single-crystalline films. PVP plays multifunctional roles in controlling the size and shape of gold nanocrystals and in inducing individual gold nanocrystals to construct 1D nanostructures. The nanoparticle self-assembling technique based on PVP offers a simple, but effective, path to organize individual gold nanoparticles into various 1D and 2D nanostructured materials.     

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.     

Protein-sheathed SWNT as a versatile scaffold for nanoparticle assembly and superstructured nanowires

One dimensional (1D) nanostructures have many possible applications in electronic, optical, and sensing devices associated with their nanosized lateral dimensions. In this regard, a general and bottom-up strategy to synthesize 1D nanoparticle arrays and conductive nanowires with a facile structural/compositional control is highly desired. We herein report a protein-sheathed single walled carbon nanotube (SWNT) that satisfies the criteria for an ideal template to assemble micron-long gold nanoparticle (AuNP) linear arrays with high structural rigidity. The resulting AuNP array has minimized inter-particle gaps, which is especially useful to template the overgrowth of Ag, Pd, and Pd/Ag metals into continuous nanowires (Au@M, M=Ag, Pd, Ag/ Pd). Our method successfully overcomes the incompatibility between carbon and metal materials, and the resulting superstructured metal nanowires have a tunable diameter below 100 nm and a shape closely replicating a SWNT. The Ag nanowires are composed of coalesced Au@Ag coreshell nanoparticles, while the Pd and Pd/Ag nanowires are made of very fine Pd nanocrystallites around the AuNP cores. These unique structural features are pivotal to various applications including surface enhanced Raman scattering (SERS), electrocatalysis, and gas sensors.     

Gold particle interaction in regular arrays probed by surface enhanced Raman scattering

Lithographically designed two-dimensional arrays consisting of gold nanoparticles deposited on a smooth gold film are used as substrate to examine the SERS effect of the trans-1,2-bis (4-pyridyl) ethylene molecule. These arrays display two plasmon bands instead of the single one observed for the same arrays of particles but deposited on indium tin oxide coated glass. Laser excitation within the short wavelength band does not bring about any SERS spectrum, while excitation within the long wavelength band yields SERS spectra with a gain per molecule rising up to 10(8). The simultaneous investigation of extinction and Raman spectra of arrays exhibiting various topography parameters enables us to suggest an interpretation for both the occurrence of the two plasmon resonances and for the high Raman enhancement. We suggest to assign the short wavelength band to a plasmon wave propagating at the gold glass interface and the long wavelength one to an air/gold surface plasmon mode modified by particle-particle interaction.     

Uniform arrays of gold nanoparticles with different surface roughness for surface enhanced Raman scattering

Uniform arrays of coarse and smooth gold nanoparticles with diameter about 130 nm were successfully synthesized through seed-mediated growth method, separately. Scanning and transmission electron microscopy (SEM and TEM) and X-ray diffraction (XRD) have been used to study the formation and structure of the nanocomposites. The high enhancement factor for surface-enhanced Raman scattering of coarse and smooth gold nanoparticles were estimated to be about 3.1 × 10⁶ and 2.0 × 10⁶, respectively. It is evident that the coarse gold nanostructures has higher influence factor than the smooth gold nanostructures. Therefore, these unique properties of the coarse Au nanoparticles appear to be very promising for applications as high-performance SERS substrates.     

Probing Innovative Microfabricated Substrates for their Reproducible SERS Activity

New types of microfabricated surface‐enhanced Raman spectroscopy (SERS) active substrates produced by electron beam lithography and ion beam etching are introduced. In order to achieve large enhancement factors by using the lightning rod effect, we prepare arrays consisting of sharp‐edged nanostructures instead of the commonly used dots. Two experimental methods are used for fabrication: a one‐stage process, leading to gold nanostar arrays and a two‐stage process, leading to gold nanodiamond arrays. Our preparation process guarantees high reproducibility. The substrates contain a number of arrays for practical applications, each 200×200 μm² in size. To test the SERS activity of these nanostar and nanodiamond arrays, a monolayer of the dye crystal violet is used. Enhancement factors are estimated to be at least 130 for the nanodiamond and 310 for the nanostar arrays.     

Synthesis and bioanalytical applications of specific-shaped metallic nanostructures: A review

Many successful synthesis routes for producing different shapes of metallic nanostructures, including sphere, rod, cube, and hollow shapes, have been developed in the past few decades. Many applications using these nanostructures have been studied because the outstanding properties of the nanostructures are not exhibited by their bulk-state counterparts. This review paper reports some recent developments in clinical and biosensor applications. The first part focused on the synthesis methods of metallic nanostructures having various shapes along with their optical properties. The second and third part is an introduction of the gold nanoparticle assemblies and arrays, explaining the conjugation methods of metallic nanostructures with biological entities. The final part reviews on the recent bioanalytical applications using various shapes of metallic nanostructures.     

Wet-chemical approach to three-dimensional gold nanocorallines: synthesis and application in surface-enhanced Raman spectroscopy

The shape-controlled synthesis of micrometer-sized gold nanocoralline was simply realized via a wet-chemical approach. The as-prepared hierarchical gold nanocorallines (HGNs) on the solid substrate were initially applied in SERS analysis with 4-aminothiophenol (4-ATP) as the probe molecule. The HGN-modified glass substrate exhibits a higher SERS effect (one order of magnitude higher) than the aggregated gold nanoparticle ( approximately 25 nm)-modified glass substrate.     

帽状金纳米结构的制备、表征及表面增强拉曼散射活性

采用真空离子溅射法在自组装的单层阵列二氧化硅纳米粒子表面沉积金薄膜, 制备了以SiO₂为核的帽状金纳米结构. 用透射电镜、扫描电镜、原子力显微镜、X 射线衍射仪和紫外-可见-近红外分光光度计对样品的表面形貌、结构及光学性质进行了表征. 以亚甲基蓝作为探针分子, 对金纳米帽的表面增强拉曼散射活性进行了研究, 结果显示, 吸附在金纳米帽上的分子拉曼散射信号得到显著增强, 增强因子达到10⁷数量级. 该基底在超灵敏生物和化学检测方面具有潜在的应用前景.     

Determination of Saxitoxin by Aptamer-Based Surface-Enhanced Raman Scattering

Saxitoxin is one of the most harmful paralytic shellfish toxins due to its high toxicity and adverse effects on the environment and human health. Aptasensors provide simple detection procedures because they have the advantages of chemical stability, easy synthesis and modification, and high convenience in signal transformation. Surface-enhanced Raman scattering (SERS) is an analytical technique that amplifies the analytical signals of molecules at extremely low concentrations, or even at the single molecule level, when the analyte is very close to rough metal surfaces or nanostructures. In this study, an SERS aptasensor is reported for the determination of saxitoxin for the first time. The optimized saxitoxin aptamer (M-30f) was modified on gold nanoparticles and served as the recognition element. Crystal violet was used as the Raman reporter without chemical bounding. The analytical principles of the aptasensor are that saxitoxin destabilized the conformations of the aptamer at high temperature conditions and altered the binding of crystal violet on the gold nanoparticles. In the presence of saxitoxin, the conformation of aptamer containing the G-quadruplex that selectively bound crystal violet unfolded to a large extent and hence the crystal violet molecules were released from gold nanoparticles with a reduced SERS signal. The effects of the gold nanoparticle size, the amount of DNA, aptamer density, sodium chloride concentration, and operation temperature upon the SERS determination were optimized. The resulting simple SERS aptasensor was developed with a satisfactory limit of detection (11.7?nM) and selectivity. The application for the analysis of real shellfish samples with simple procedures demonstrates that this SERS aptasensor is promising for on-site applications.     

Nanosphere arrays with controlled sub-10-nm gaps as surface-enhanced raman spectroscopy substrates

We demonstrate a convenient and cost-effective chemical approach for fabricating highly ordered Au nanoparticle arrays with sub-10-nm interparticle gaps. Near-field enhancements inside the interparticle gaps create uniform periodic arrays of well-defined "hot spots" exploitable for large surface-enhanced Raman spectroscopy (SERS) enhancements. A cetyltrimethylammonium bromide (CTAB) bilayer surrounding each individual nanoparticle upon array crystallization is responsible for this periodic gap structure; displacement of the CTAB by smaller thiolated molecules does not affect the structural integrity of the arrays. As SERS substrates, the as-fabricated Au nanoparticle arrays exhibit high SERS sensitivity, long-term stability, and consistent reproducibility.     

Thin metal nanostructures: synthesis,properties and applications

Two-dimensional nanomaterials, especially graphene and single- or few-layer transition metal dichalcogenide nanosheets, have attracted great research interest in recent years due to their distinctive physical, chemical and electronic properties as well as their great potentials for a broad range of applications. Recently, great efforts have also been devoted to the controlled synthesis of thin nanostructures of metals, one of the most studied traditional materials, for various applications. In this minireview, we review the recent progress in the synthesis and applications of thin metal nanostructures with a focus on metal nanoplates and nanosheets. First of all, various methods for the synthesis of metal nanoplates and nanosheets are summarized. After a brief introduction of their properties, some applications of metal nanoplates and nanosheets, such as catalysis, surface enhanced Raman scattering (SERS), sensing and near-infrared photothermal therapy are described.     

Facile hydrothermal synthesis of 3D hierarchical Bi2SiO5 nanoflowers and their luminescent properties

Facile hydrothermal synthesis of novel hierarchical flowerlike Bi₂SiO₅ nanostructures consisting of single-crystal nanosheets is reported using polyvinylpyrrolidone (PVP, K30) as capping reagent in the presence of NaOH. The obtained products are systematically characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy and Fourier transform infrared spectroscopy. Control experiments are carried out to investigate various factors that affect the morphology and size of the products. The results indicate that the nucleation and growth of the flowerlike nanostructures are dominated by a nucleation–dissolution–recrystallization growth mechanism. It is demonstrated that the concentrations of PVP and NaOH play important roles in the formation of the hierarchical nanoflowers. Moreover, the room-temperature photoluminescence properties of the Bi₂SiO₅ nanoflowers are also investigated.     

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