pH-triggered assembly of gold nanorods

The self-assembly of surfactant-protected gold nanorods (aspect ratio 3.3 +/- 0.3, 20.6 +/- 5.5 nm width, and 67.5 +/- 9.0 nm length) into ordered structures using adipic acid is presented. As made, the gold nanorods are coated with cationic surfactant, which gives them a net positive charge in aqueous solution. The pH-dependent assembly is directed by electrostatic interactions between the positively charged nanorods and negatively charged, deprotonated adipic acid. Absorption spectra and light scattering measurements of these nanorods suggest that aggregation is initiated in solution in the presence of adipic acid at pH 7-8, but not at pH 3, to form small assemblies of nanorods. Zeta potential measurements show that the assembly is significantly less positively charged in the presence of deprotonated adipic acid than when adipic acid is fully protonated.     

Growth of gold nanorods and bipyramids using CTEAB surfactant

Gold nanorods and bipyramids have been synthesized using the seed-mediated approach in aqueous cetyltriethylammonium bromide (CTEAB) solutions in the presence of silver nitrate. Gold nanoparticle seeds that are stabilized with either CTEAB or sodium citrate have been used. The use of the CTEAB-stabilized seeds gives gold nanorods in high yield in one step with the longitudinal plasmon wavelength ranging from 750 to 1030 nm, depending on the amount of the seeds. The longitudinal plasmon wavelength can be extended to 1100 nm by the use of a two-step growth method. The growth of gold nanorods in CTEAB solutions takes 5-10 h, more than 5 times slower than that in cetyltrimethylammonium bromide solutions at the same concentration of surfactants. The use of the citrate-stabilized seeds gives both gold bipyramids and a small percentage of gold nanorods. The longitudinal plasmon wavelength of the bipyramids is tunable from 700 to 1100 nm by varying the amount of the citrate-stabilized seeds. The growth of gold bipyramids takes more than 1 day. Transmission electron microscopy characterizations reveal that the gold nanorods grown from both types of gold nanoparticle seeds are single-crystalline and that the gold bipyramids are penta-twinned.     

Growth of gold nanorods in gelled surfactant solutions

Gold nanorods have been actively studied for new nanotechnological materials and industrial applications. It is well known that gold nanorods grow spontaneously in surfactant solutions, and a number of procedures for their preparation have been reported; however, the factors that determine the morphology have not been well understood. In this study, we observed the time series of the growth process of gold nanorods in gelled surfactant solutions by completely stopping the growth reaction. This growth process was compared to that in solution without gelation. The comparison indicates that the self-assembly of surfactant molecules affected the resulting shape, especially the short-axis length, of the nanorods. Small-angle neutron scattering (SANS) experiments revealed that the gelled solutions form lamellar structures, whereas nongelled systems form spherical micelles. On the bases of these results, we present a model showing that the short-axis length of gold nanorods is affected by a decrease in the spontaneous curvature of the outer surfactant layer and/or an increase in the bending modulus of the surfactant membrane neighboring the gold surface.     

Precise placement of gold nanorods by capillary assembly

Capillary assembly was explored for the precise placement of 25 nm × 70 nm colloidal gold nanorods on prestructured poly(dimethylsiloxane) template surfaces. The concentration of nanorods and cationic surfactant cetyltrimethylammonium bromide (CTAB), the template wettability, and most critically the convective transport of the dispersed nanorods were tuned to study their effect on the resulting assembly yield. It is shown that gold nanorods can be placed into arrayed 120-nm diameter holes, achieving assembly yields as high as 95% when the local concentration of nanorods at the receding contact line is sufficiently high. Regular arrays of gold nanorods have several benefits over randomly deposited nanorod arrangements. Each assembled nanorod resides at a precisely defined location and can easily be found for subsequent characterization or direct utilization in a device. The former is illustrated by collecting scattering spectra from single nanorods and nanorod dimers, followed by subsequent SEM characterization without the need for intricate registration schemes.     

Preferential end-to-end assembly of gold nanorods by biotin-streptavidin connectors

A major challenge in nanoscience and nanotechnology is the rational assembly of nanoscale objects. Here we report that gold nanorods, aspect ratio 18, can be functionalized with a biotin disulfide, and subsequent addition of streptavidin links the rods together in an end-to-end manner much more often than expected.     

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.     

Controlled side-by-side assembly of gold nanorods and dye molecules into polymer-wrapped SERRS-active clusters

The controlled side-by-side assembly of gold nanorods in solution together with Raman reporter dye molecules to create small SERRS-active clusters stabilised by a surrounding polymer layer is demonstrated. This promising new class of nanotags offers several advantages over spherical nanoparticles for bioimaging and is of potential importance for a wide range of plasmon-enhanced spectroscopies and can also serve as building blocks for more complex solution-phase nanostructures.     

A calorimetric investigation of the assembly of gold nanorods to form necklaces

Interaction of gold nanorods with cysteine as well as 3-mercaptopropionic acid (MPA) has been investigated by isothermal titration calorimetry (ITC), in combination with electronic absorption spectroscopy and electron microscopy. The assembly process with MPA shows two steps, the first due to the binding of MPA to gold nanorods through the sulfur atom, and the second due to assembly of the MPA capped gold nanorods through the formation of cyclic hydrogen bonded dimers between the MPA molecules. In the case of cysteine only a single step is observed in ITC, due to the binding of the molecules to gold nanorods.     

The importance of the CTAB surfactant on the colloidal seed-mediated synthesis of gold nanorods

Gold nanorods were synthesized by the colloidal seed-mediated, surfactant-assisted approach [Gou et al., Chem. Mater. 2005, 17, 3668-3672] using CTAB (hexadecylcetyltrimethylammonium bromide) obtained from ten different suppliers. The yield of gold nanorods depended strongly on the CTAB used: with the same recipe, three of the CTABs did not yield nanorods and produced only spherical gold particles, whereas the other CTABs yielded nanorods with nearly 100% yield. These results suggest that an impurity in the CTAB is very important for nanorod formation.     

Colorimetric determination of ferrous ion via morphology transition of gold nanorods

A colorimetric method is described for the determination of ferrous ion (Fe²⁺) with high sensitivity and selectivity. The method is based on catalytic etching of gold nanorod (NR). In an acid condition, Fe²⁺ reacts with H₂O₂ to produce superoxide radical (O₂ ^??) that etches gold NRs from the low energy surface along the longitudinal direction preferentially. As a result, the changes in the absorption spectrum and color of gold NR can be measured and also can be detected visually. Under the optimal conditions, the assay has very low detection limit (13.5 nM) and a linear response in a concentration range of 75 to 1 μM. The method was applied to the determination of Fe²⁺ in spiked samples of fetal bovine serum and also transferred to a kind of test stripe for use in fast practical applications. A unique colorimetric sensing method is demonstrated for the colorimetric detection of Fe²⁺, again based on the oxidation of gold nanorods which leads to the blue-shift of the absorption.

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Graphical abstract A unique colorimetric sensing method was shown for the colorimetric detection of Fe²⁺. Fe²⁺reacts with H₂O₂ to generate superoxide radical that oxidize gold nanorods. This leads to a color change from blue-green to pink.

     

Immobilization of gold nanorods onto acid-terminated self-assembled monolayers via electrostatic interactions

We report the immobilization of gold nanorods onto self-assembled monolayers (SAMs) of 16-mercaptohexadecanoic acid (16-MHA). The simple two step protocol involves formation of a SAM of 16-MHA molecules onto gold-coated glass slides and subsequent immersion of these slides into the gold nanorod solution. The nanorods, formed by a seed-mediated, surfactant-assisted synthesis protocol, are stabilized in solution due to surface modification by the surfactant cetyltrimethylammonium bromide (CTAB). Attractive electrostatic interactions between the carboxylic acid group on the SAM and the positively charged CTAB molecules are likely responsible for the nanorod immobilization. UV-vis spectroscopy has been used to follow the kinetics of the nanorod immobilization. The nature of interaction between the gold nanorods and the 16-MHA SAM has been probed by Fourier transform infrared spectroscopy (FTIR). The surface morphology of the immobilized rods is studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM) measurements. SEM was also used to determine the density of the immobilized nanorods as a function of the pH of immobilization. Control over the surface coverage of the immobilized gold nanorods has been demonstrated by simple pH variation. Such well-dispersed immobilized gold nanorods with control over the surface coverage could be interesting substrates for applications such as surface-enhanced Raman spectroscopy (SERS).     

Reversible assembly and disassembly of gold nanorods induced by EDTA and its application in SERS tuning

A facile and reversible method for assembling and disassembling gold nanorods (GNRs) using a common chelating agent, ethylenediaminetetraacetic acid (EDTA), is reported. Assembly was induced by the electrostatic interaction between the cetyltrimethylammonium bromide (CTAB) bilayer present on GNRs and EDTA. At lower concentrations of EDTA, end-to-end assembled chains were formed. At higher concentrations of EDTA, these chains come together to form sheet-like structures. The complex of CTAB and EDTA, being labile, disassembles in the presence of stronger chelating agents. Upon addition of metal ions having higher formation constants, EDTA detaches from the GNRs and forms stronger complexes with metal ions, resulting in disassembly. Characteristic changes were observed in the UV/vis spectra. Addition of EDTA resulted in a red shift of longitudinal surface plasmon (LSP) resonance at lower concentrations, indicating an end-to-end assembly. At higher concentrations, the characteristic of side-by-side assembly was seen in the UV/vis spectra. TEM analysis proved the existence of end-to-end chains at lower concentrations of EDTA and side-by-side assembled sheet-like structures at higher concentrations. The addition of metal ions induced disassembly. Even 2 ppb of metal ion was detected using the spectral changes. Disassembly was studied in detail, taking Pb(II) as the model system. Upon addition of Pb(II), TSP showed a blue shift and decreased in intensity while the LSP showed a red shift and increased in intensity. A new peak at a higher wavelength region emerged, pointing to the existence of both side-by-side and end-to-end assembly in the system. TEM analysis showed that the disassembly involves the formation of bundled chains which may be the reason for the observed spectral changes. Surface-enhanced Raman scattering (SERS) activity of the system could be tuned by controlling the concentration of EDTA and the metal ion, Pb(II).     

Anisotropic assembly of gold nanorods assisted by selective ion recognition of surface-anchored crown ether derivatives

Gold nanorods (NRs) mixed with crown ether derivatives exhibited the efficient and selective recognition of Na+ and K+ ions, which were detected by localized surface plasmon absorption in response to dispersed and aggregated gold NRs. Furthermore, in the aggregates preferential end-to-end or side-to-side assembly of NRs was observed which was dependent on the additive concentration.     

Ligand customization and DNA functionalization of gold nanorods via round-trip phase transfer ligand exchange

Customizable ligand exchange of gold nanorods (NRs) is described. NRs are synthesized with the cationic surfactant cetyltrimethylammonium bromide (CTAB) which is exchanged with thiolated ligands that enable suspension in buffer. Exchange is achieved by a two phase extraction. First, CTAB is removed from the NR-CTAB by extracting the NRs into an organic phase via the ligand dodecanethiol (DDT). The NR-DDT are then extracted into an aqueous phase by mercaptocarboxylic acids (MCA), HS-(CH 2)n -COOH (n = 5, 10, and 15). Ligands can be further customized to thiolated poly(ethylene glycol), PEG MW (MW = 356, 5000, and 1000). Ligand-exchanged NRs (NR-MCA and NR-PEG(MW)) are stable in buffer, do not aggregate, and do not change size upon ligand exchange. They can be run in agarose gel electrophoresis with narrow bands, indicating uniform charge distribution and enabling quantitative analysis. DNA functionalization of NR-MCA is straightforward and quantifiable, with minimal nonspecific adsorption.     

Enrichment and sensitive detection of polyphenolic compounds via β-cyclodextrin functionalized fluorescent gold nanorods

Microchimica Acta - We report on a simple and rapid method for the enrichment of polyphenolic compounds (pPhCs) by means of gold nanorods whose surface was functionalized with a monolayer of...     

Photochemical synthesis of gold nanorods

Gold nanorods have been synthesized by photochemically reducing gold ions within a micellar solution. The aspect ratio of the rods can be controlled with the addition of silver ions. This process reported here is highly promising for producing uniform nanorods, and more importantly it will be useful in resolving the growth mechanism of anisotropic metal nanoparticles due to its simplicity and the relatively slow growth rate of the nanorods.     

Photochemical control of molecular assembly formation in a catanionic surfactant system

Photochemical control of vesicle disintegration and reformation in aqueous solution was examined using a mixture of 4-butylazobenzene-4'-(oxyethyl)trimethylammonium bromide (AZTMA) as the photoresponsive cationic surfactant and sodium dodecylbenzenesulfonate (SDBS) as the anionic surfactant. Spontaneous vesicle formation was found in a wide-ranging composition of the trans-AZTMA/SDBS system. AZTMA molecules constituting vesicles underwent reversible trans-cis photoisomerization when irradiated with ultraviolet and visible light. Transmission electron microscopy observations using the freeze-fracture technique (FF-TEM) showed that UV light irradiation caused the vesicles to disintegrate into coarse aggregates and visible light irradiation stimulated the reformation of vesicles (normal control). A detailed investigation of the phase state and the effects of UV and visible light irradiation on the AZTMA/SDBS system with the use of electroconductivity, dynamic/static light scattering, and surface tension measurements and FF-TEM observations revealed that in the AZTMA-rich composition (AZTMA/SDBS 9:1) a micellar solution before light irradiation became a vesicular solution after UV light irradiation and visible light irradiation allowed the return to a micellar solution (reverse control). Thus, we could photochemically control the disintegration (normal control) and reformation (reverse control) of vesicles in the same system.     

Morphological and dimensional control via assembly of polyaniline crystals

A facile and general route to a new generation of polyaniline(PANI)-citric acid(CA) crystals such as 2D nanoplates, 2D nanosheets and 3D microrods self-assembled by the π-π stacking interaction is reported. Dramatic, 3D rectangular shaped microrods and 2D nanosheets are single crystals indicated by SAED patterns and HRTEM images. Moreover, the method does not depend on any specific equipment or heating, cooling and complex procedures. The novel polyaniline crystals will be useful for next generation organic electronics such as nano-transistors.     

Simultaneous identification of point mutations via DNA ligase-mediated gold nanoparticle assembly

Multiplex single nucleotide polymorphisms analysis has found a great demand in human genetics and pharmacogenetics. The present study reports a novel approach for a genotyping assay that could achieve simultaneous identification of multiple point mutations via a ligase-mediated gold nanoparticle assembly. Based on the allelic specificity of DNA ligase, gold nanoparticles modified by oligonucleotide probes perfectly matched to the DNA targets were assembled into a thermally-stable aggregate, while a single-base mismatch would result in the dissociation of the gold nanoparticle assembly at high temperature. Then, DNA targets and their point mutations could be differentiated using a multi-step temperature elevation analysis monitored by ultraviolet-visible measurements. This approach offered a direct colorimetric discrimination of multiple point mutations without stringent temperature control. The proposed approach is demonstrated using a model system for the identification of single-base mutations in codon 17 and position -28 of the beta-thalassemia gene. The results reveal that the wild and the mutant types could be simultaneously determined successfully. Owing to its ease of operation and high specificity, it was expected that the proposed procedure might hold great promise in both research-oriented and clinical genomic assays.